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Please be aware that all missing pages were supposed to be blank. ORGANIZERS
Russian Academy of Sciences (RAS)
Division of Cemistry ad Material Sciences
Researc Cuncil Oil Organic ad Or-anoelenient Cenlistly
AX Nesrnevario, Institute of Organoelerrient Compounds
N.D. elinsky Institute of Organic Chemistry
N.S. Kurnakm Istitute of General and Inorganic Cemistry
Institute for Physical Chemistry of Ceramics
M.V. Lomoiiosov iMoscow State University
St"ite ScIcimfic-Research Istitute of Cliernisti- ad Technology of Organoelerrient Compounds
,,VIAM , State Research Center
SPONSORS
I U PAC
U N ESCO
Ministry of Industry, Science ad Technology of te Russian Federation
RLISSIaii Foundation for Basic Research
BORAX Europe Ltd.
AV!;'WOR OAO WELCOME TO IMEBORON XI
Dear Colleazues,
Welcome to the XIth International Conference onBoron Chemistry in Moscow.
Boron Chemistry as a connecting bridge between many fields aintains one of the leading positions in modem chemistry. This is reflected both y an ncreasing number of publications on organoboron, carborane and metallacarborane chemistry and a lot of boron conferences of International, European and National formats. We feel very much honored that the MEBORON XI, the first Iternational Conference on Boron Chemistry in the XXI Century, will be held in Moscow, te Capital of the Russian Federation. This Moscow Conference will take place in the conference halls (the Red and Blue oes) of te main building Of th Rsian
Academy of Sciences, 32a, Lemnsky prospect, 3 d floor. T ivited 35 inutes long) and contributed 20 minutes Iona) lectures will poceed in two parallel sessions A and B. There will be two poster sessions displaved i te Foyer near te Lecture Halls. Soft drinks, coffee and tea will be aailable in the fovc - dUrin, tile breaks. For all participants, lunches will be served at the restaurant ofth sme building.
The OraanizinL Cornmi tr c e rrABLE OF CONTENT'S
GENERAL INFORMATION Introduction B I E130RON Sites Reuistration desk Participants' badges Alail and ',Nlessages Telephones Lunches Ack-nowleduements Internationai Committee Oroanizinc, Committee NationalAdvisory Committee
SOCIAL EVENTS AND ACCOMPANYING PERSONS' PROGRAMME
SCIENTIFIC PROGRAMME Oral pogramme Posters
LOCAL MAP GENERAL INFORMATION
Introduction
The IMEBORON-XI conference on Boron Chemistry is sponsored by 1UPAC, UNESCO, Ministry of Industry, Science and Technology of the Russian Federation, Rssian Academy of Sciences, Russian Foundation for Basic Research, JSC Aviabor" and Borax Erope Ltd., and takes place at the Main Buildin- of the Russian Academy of Sciences from Monday 29 July to Friday 2 August
2002 wth participants foregathering on Jly 28.
Imeboron Sites I Castle Liblice near Prague,Czechoslovakia Jaromir Ple ek 11 Leeds Egland Norman N. Greenwood III Munich d Eltal, Gcrinan-v Heinrich N6th IV Salt Lake City ad Snoi -bird, US.4 Robert W. Parry V Swansea, fVales, United Kin-doni Andrew Pelter VI Bechyne ear Tabor Cechoslovakia Bohumil Stibr VII Torlin, Poland
Marek Zaidle ,vicz VIII Knovville, Tennessee. USA George W. Kabalka IX Heidelbero, Germanv Walter Sebert Durhani, United Kin-dom Kenneth Wade XI -Afoscoit%Russian Federation Yuri BLibnov Reoistrationt, desk
The ain Re-istration desk is situated in te foyer of the A. N. Nesmeyanov Institute of Organoelemen Cmpounds, 28, Vavilov St. (Moscow). The scientific sessions (A and B) will be eld at the conference halls of the Russian Academy of Sciences ain building P floor, 32a Leninsky prospect, Moscow). At the sarne place posters are been,, ounted. The Registration desk will be open from 200 till 22.00 on Sunday 28 July.
Pai-ticipants' badges6
Clippin-on bad2es have been sued for all participants and accompanvingpersons. Participants are kindl rquested to war their bad-es troughout the rneeting. For the purposes of easy identification h folio" ng colour scheme is being used:
"Iclilv arlicipants Blue
.-h collipani i- PerSons ffinte
C0117121ittee Green
Assistants Red
Nlail and Messages
To all participants, letters ShOUld be addressed to the irldividual:
VNIEBORON XI A. N. Nesinevanov Institute of Organoelernent Compounds Vavilov Street 28, 119991 Moscow V-334, GSP-1, Russian Federation E-rnail: hneboron(q7 ineos.ac.ru
Telephones
There re card-operated elephones. for outgoing calls. available in hotels and postoffices. Cards for the [P tclephony are also available. Lunches Lunches, admissions to which is uovemed bv TICKET ONLY. will take lace nthe res'MUratit f the Main bi-111dinLy of the RAS.
Acknowledgements
The Organizing Committee extend thanks to the Russian Academy of Sciences or providing the Conference with comfortable halls in the Main Buildin- of the RAS and all the Oruanizers and sponsors for the prolific partnership.
International Committee
V. 1. Bregadze (Russia) H. N6th (Germany) H. C. Brown (USA) P. Paetzold (Germany) Yu. N. Bubnov (Russia) A. Pelter (UK) R. Contreras (Mexico) S. G. Shore (USA) Y. Do (Korea) W. Siebert Germany) N. N. Greenwood (UK) B. tibr (Czech Rep.) R. N. Grimes (USA) A. Suzuki Japan) M. F. Hawthorne (USA) F. Teixidor Spain) G. W. Kabalka (USA) K. Wade (UK) W. N. Lipscomb (USA) Y. Yamamoto Japan) M. Zaidlewicz Poland)
Organizingt5 Committee
Yurii N. Bubnov Chairman. L,%,'EOS R IS Vladimir 1. Bregadze Vice-chairman. NEOS RS Pyotr M. Valetsky Vice-chairman. NEOS RS Valentina A. 01'shevskaya Secretai-v. LVEOS PNS loor T. Chizhevsky INEOS R,-I S Vladimir A. Dorokhov i0c RAS Mikhail E. Gursky 10C RAS Valerii N. Kalinin INEOS RAS Alexander R. Kudinov INEOS RA S Larisa A. Leites INE,0) RA S Dmitril G. Pershin IOC RAS N.itional Advisory Committee
Yti. N. Btibnov V. 1.Bregadze E. N. Kablov K. A. SoIntsev N. T. KLIznetsov P. A. Storozheriko V. V. Lumn P. M. Valetsky 0 M Nefedov V. V. Volkov G. F. Teresliclienko IL. . Zakharkin
6 SOCIAL EVENTS
Sunday 28 July 19.00-22.00 Reception for the participants at A. N. Nesmeyanov Institute of Organoelement Compounds of the RAS.
Wednesday 31 July 13.00 Informal sightsecing tour around Moscow: "Kolomenskoye" Reservation-Museum, a boat trip along the Moskva-river. Buses will depart frorn the "Sputnik"-hotel at 13.00. The excursion includes dinner at the 'Sputnik"-hot,21. Thursday I August 18.00 Conference Dinner.
ACCOMPANYING PERSONS'PROGRAMME
Following Tours are suggested for accompanying persons to attend:
lt7 - In a) Moscow Sightsecing b) The State Armoury Chamber of the Moscow Kremlin c) The State Tretyakov Gallerv SCIEN rrIFIC PROGRAMME: 1 Ivited and contributed lectures
JuIN7 29, Nonday
9.00 Opening Ceremony
Introductorv remarks: Yu. Bubnov, Chairman IMEBORON Xi Remarks on WPAC Meetin-s: Deleoate, nternational Union of Pure ad Applied Cemistry
Chairman: R. E. Williams 9.-)o [B-I V.N. Kalinin: "Prof. Leonid 1. Zakharkin's contribution o he carborane chemistry" IA-I M. Frederick awthorne: "Further ad\ ances at the iterface of boron and carbo cemistries"
10.30 Coffee-Tea
11.00 IA-2 Ken Wadt-: -Evoiving patterns in boron cluster chemism a reassessment of some old oeneralizations" I.-, I B-2 Botiumil Stibr: "NeNN t\pes of carboranes and phosphacarboranes" 12.10 Lunch
Chaii-lnaiv P. Paetzold Chaii-nian.-M. ZaIdlewich
14.00 IA-3 kk . Siebert: -Polvboranes. carboranes and - B-3 Geor-e W Kabalka: The use of oroanoboron heteroboranes" halides in or-anic snthesis" 14.3 5 CA-] Robert Greatrex: -Cluster fluxionality and CB-I flya D. Gridnev: "Search for intermediates in rearrangement in ten-vertex closo the catalytic hdroboration with QUINAP and dicarbaborane sstems" QUINAPO liands" 45 CA-2 T. JelineL: "Prouress in the chemistry of eght CB-2 Vladimir Gevor-yan: "Novel applications of and nine-vertex nonocarbaborane anions" perfluorinated arylboron catalystsin organic synthesis"
15.15 Coffee-Tea Coffee-Tea
15.45 Posters Posters
8 July 3, Tuesdav
Chairman: L. Barton Chairmaw G. W. Kabalka
9.00 IA-4 John D. Kennedv: Intramolecular and I B-4 Donald S. atteson: -Ne % s% mmoric syntheses supramole-cular cluster interactions" with boronic esters and fluorohorancs" 9.35 CA-3 Mamoru Shimoi: "Reactivity of the cluster CB-3 Hirovuki Nakamura: --Synthesis and hiolo-ical core of ruthenaboranes toward phosphorus evaluation of boron containing EGI R protein compounds" tyrosine kinase inhibitors" 9.55 CA-4 Youngkyu Do: "Luminescence of roup 4 CB-4 V. A. Ponomarev: and (R)-(-)-2-methyl- metal carborane complexes" 1-boraadamantanes" 10.15 Coffee-Tea Coffee-Tea Chairman: W. Siebert Chairman: Y. Endo
10.45 IA-5 Narayan S. Hosmane: "Recent advances in I B-5 Marek Zaiclle kicz: "Enolboration of conjugated the chemistry of carboranes and ketones. synthesis of boronic acids, and P-ainino metallacarboranes" alcohols" 120 CA-5 Alexander V. Safronov: Closo- CB-5 Victor A. Bratisev: Sulphur introduction into
iridacarboranes ith carboc clic ligands a B 2H 1,2 by [(NH,),CSjCL- - a nev halogen- new one-pot synthetic procedure" like lectrophilic aoent" 11.40 CA-6 B. GrUner: -Ncw functionalized cobalta- CB-6 Stefan SjOberg: Radioli-flogenated polyhedral bis(dicarbollide)(I-) ions" boron clusters or use i tar-eted oncolo(Ocal nuclide therapC
12.00 Lunch Lunch Chairnian: N. S. Hosmane Chairman.- D. E. ,11LIfniann
14.00 IA-6 Alan J Welch: Supraicosahedral I B-6 P. VeeraraLhaan amachandran: -S,,ritheses of (metalia)carboranes" biological] acti%e olecules ia or-anoboranes" 14.35 CA-7 Yasuro Kawano: Borl complexes and CB-7 Andreas Franken: ar-,lated [clo.s-o-l- cationic borane a complexes of manganese: CBIH,2] -and [closo I C Bj I anions" heterolytic clewage of the metal- coordinated B-H (Ybond" 14.55 CA-8 B. Brellochs: -Snthesis of new CB-8 V.A. 01'shevskava: -Boron-containing hydroxylated LOSo-dodecaborates BH,,- porphyrins a ne\v snthetic anproach"
n(OH),,2-" 15.15 Coffee-Tea Coffee-Tea
15.45 IA-7 Zuowei Xie: "Arachno-carborane anions and I B-7 A. Berridt: -T %o-electron aromatics containing
their metal complexes's three and four ajacent boron atoins" 16.20 CA-9 [-or T. Chizhevsky "Metal-assisted CB-9 Ruslan M. Nlinyacv: -Flernentoorganic pGlvhedral contraction reactions of mono- compounds with main-I-OUP hypercoordinated and dicarbon carborane svstem derived centers" from nidolcloso-CB1,), nido-CB.. ni(lo-CBs and exo-n0o-CB,)M (M=Os)" July 31, Wednesday
Cliciii-m(m.- L. G. Sneddon Chah-man.- Y. Yarnamoto
9.0( IA-8 Russell N. Gimes: Synthesis and I B-8 Manfred Bochmann: "Clicinistry of lectron- properties ot'linear, branched and cyclic deficient mtal alkyl complexes of early
niciallacarborane oligomers" transition nictals: reactivity of the catalyst activator B(U )3"
L). CA-10 Mark Thornton-Pett: "Borane based CB-10 Michael A. Beckett: "New aspects of boroxine dihdro-en-bondcd nemorks" chemistry"
9. 5 coffee-Tea Coffee-Tea
I(.2 IA-( i rancesc Telxidor: Boron clusters. do I B-9 Yasuvukj Endo: UtilitN of boron clusters for thc\ receive the deserved iterest?" drua desian: selective estro-en receptor
modUkItOr (serm I)bearin- carborane as a h\drophobic skeletal structure"
I I (( CA -I I Radim \;esr)alec: -Chiral separations of CB-1 I Ole- L. Tok: "The 1.1-or-anoboration of hii lu,)ier horanes" o1cfinic derivatives of tin"
1 1 2 Lunch Lunch
Excursion August 1, Thursday
Chairman: J. D. Kennedy Chairman.-D. S. Matteson 9.00 [A-10 Lawrence Barton: "Reactions ot boranes and IB-10 Yoshinori Yarnamoto: Carborane---adolinium metallaboranes with phosphines" binary system as a MR imagin, boron carrier" 9.35 CA-12 Alexander R. Kudinov: "Direct insertion CB-12 Piotr Kaszynski: Investigation of electronic into closo-metallacarboranes" interactions in derivatives of closo-boranes"
9.55 CA-13 Clara Viftas: "Synthesis and reactivity of CB-13 E. Hey-Hawkins: "Synthesis and coordination new halogenated boranes and carboranes" properties of carbaboranylphosphines" 10.15 Coffee-Tea Coffee-Tea Chairman: F. Teixidor Chairman.-A. Bemdt 10.45 1A-1 I Peter Paetzold: Opening of the closo-NB [B- I D. E. Kaufmann: "The B, N chromophoric clusters by bases: mechanism" system" 11.20 CA-14 Libor Mikul8ek: "First CB-14 D. G. Pershin: "Allylboration of nitroso diarsadicarbaboranes. analo-ues of the compounds" eleven-vertex tetracarbaborane CBH series" 11.40 CA-15 1-or Sivaev: Svnthesis of functional CB-15 A. Semioshkin: Synthesis ofthe novel derivatives of the [2-CBH I,,]' anion" carboranes based oil I bronionlethy I-o- carborane" 12.00 Lunch Lunch 14.00 Posters Posters 18.00 Conference Dinner August 2 Friday
Chah-man: R. N. Grinies 9.00 IA-12 Larry G. Sneddon "Molecular ad polymeric pecursors to bron crbide nanofibcrs. nanocylinders and nanoporous ceramics" Q.35 CA 16 Michael G. S. Londesborouoh: "New advances i macropolyhedral boron-containing cluster chemistry" 9.5 5 CB-16 WaN P. Simk "Studies on new boron complexes of bologically active ligands" 10.15 Coffee-Tea
10.45 IB-11 Detlef Gabel: Rearran-ements in the nona- and nonaazaborane clusters" 11.20 IA-13 Sami Ook Kan-: "Reactions of sily]-o-carboranes " ith transition-metal complexes: formation of stable transition-nietal sil I complexes" I 1.55 Closino Remarks followed bv Lunch
2. Posters
There xNIII be t o formal poster viewing sessions during the course of the conference, as follows:
Poster Session I - 1 5.45 o Monday 29 July
Poster Session 11 -- 14.00 on Thursday I August
Presenters sould refer to the main author/presenter index in the book of abstracts to secto wich
session their poster has been allocated.
POSTER SESSION I P-1 - P-44)
POSTER SESSION 11 (P-45 - P87)
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ABSTRACTS FOR INVITED SPEAKERS
AND CONTRIBUTED LECTURES
7 IB I RU0410002
PROF. LEONID 1. ZAKHARKIN'S CONTRIBUTION TO THE CARBORANE CHENItsTRY
V. N. Kalinin and V. A. 01'siievskava
A N. Nesmeyanov histitute of 01-gaizoelement Compounds,28 Vavilov Str. 119991 MoscowRussian Federation,e-mail: vkalin Civineos.ac.ru
Prof L. 1. Zakharkin's contribution to a discovery, formation, and development of tile chemistry of polyhedral carboranes, icosahedral o-, m-, p-Q)BIOH12 is considered. The main results of his research in the field are as follows. Methods for preparation of both C- and B-functionalized carboranes were developed and the cemical properties of isomeric carboranes investigated. Te behaviour featares of functional groups at six-coordinated carbon and boron atoms in comparison with usual oroanoboron compounds were discovered. Carboranes were demonstrated to have high thermal stability wth the equilibrium between meta and para-isorners taking place at elevated temperature. Tile metallation procedures for carboranes with both BuLl and alkali metal arnides were eaborated. The etaliated intermediates were used for preparation of the variety of carborane derivatives with C-C, C-0, C-N, and C-M (M As, H, P, Pb, Sb S) bonds. Cupriocarboralles reveal sonic features which are not attributed to usual organocopper compounds. The copper derivatives were used for preparation of both bis- and tetrakis carborane compounds. A relationship between the electronic effect of the carboranyl niolety on the attached functional group depending on the location of te substituent at the carborane core was discovered. For example, o-carboran-9-yi group is a powerful electron donating substitUent (T, 0.23) nlike o-carboran I yl one which is a powerful electron acceptor 67 = 0.39). Both thermodynamic and kinetic acidity of the isomeric carboranes were measured. The C-H bond acidity was shown to reduce in the ortho > eta > para sequence. It was fund that all cosahedral cafboranes are capable of hvdro2cn bonds fonniation wth aprotonic solvents sch as DMFA and DMSO. The abliltv of arborane core to accept electrons producing the dcarbadodecaborate dianions as demonstrated. the electron affinity of carboranes decrease in the orlho > meta para sequence. Prof. L. 1. Zakharkin is one of the pioneers of the chemistry of x-coordinated boron compounds containing B-C. B-N. B-0. B-S, B-metal bonds. lic irnonsirated he carboranes bearin- various functional --roups rveal properties characteristic ,or usuai funcrionahzed oruanic compounds. But. in adition. some new reactions were discovered. These are ,he reaction ot dicarbadodecaborate dianions prepared bv a reduction of carboranes) with NH lading to 3_ amino-o-carboranes on te followino oxidation of the reaction mixture and a preparation of te B- alkyloxy derivatives or B-alkVl/aryl carboranes from aidehydes or organolithium and agnesium Compounds respectively in the same conditions. Pd-Catalyzed cross-coupliny reactions of - iodocarboranes, B-iododicarbaundecaborates or B-iodornetallacarboranes wth both Grignard and organozinc reagents yielding a variety of B-substitu -ted polyhedral boron cornPOUnds were fund. The cyclomatallation reactions of carboranes were investigated. Tile raction cn proceeds either with retention of he oxidation state of tle metal atom or Nvith a ncrease of te oxidation state by 2 points. The carboran drivatives bearina tile B-transition metal (Fe, Re, n, Re, Ru, Os, Ri. fr.. Pd, Pt) bonds were snthesized. A number of carborane containing onomers were obtained. Tey were used for preparation of polymer inatherials o vrious vises. In ddition, sonic ftinctionalized carborane derivatives for boron eutron capture terapy (BNCT) were designed.
19 IA-1 RU0410003
FURTHER ADVANCESATTHE INTERFACE OF BOIZON AND CARBON CHEMISTRIES M. Frederick Hawthorne
Department of Clicinistry anti Bochetniswi , University of California, Los,4ngeles, California. US.4,e-mail.- nzfli( chcin.ucla.edu
The confluence of or-anic chemistry wth te chemistry of the polyhedral boranes has ided bases of a ne,,N- field of chei-nisn (Organoborane Chemistry of the Second Kind) important o ftindann; mal kno, vledQe as wel, as several areas of emer-in- technology ,2]. As exa-mvies of this d\c1or)inL fd of hernistry one rnav cite te recent discovery of 111uhipie orpnoi -unctionalized polyhedral borarto derivatives (closorners) such as [closo-
B I((OR) 2 2- \\here R = alkyl, acyl or carbarnoyl. These species have provided new
Chernisti-v ad mny potential applications in medicine and aterials science. In addition, lincar rod-Ilike molcculcs (carborods) comprised ofp-carborane -tied acctylenic construction module h\ bee uder investigation for some time. Carborods are quite robust and suggest themselves as components of molecular electronic devices ad nanornachines. Tese ad other areas of related research will be reported.
References
1. il. FFCCICI-Ick awthorne, Carborane Chemistry at Work and at Play," Proceedings of the Ninth International Meeting on Boron Chemistry Advances in Boron Chemisoy, Special PUblication No. 201, Edited by W. Siebert, the Royal Society of Chemistry: Cambridge, 261 1996).
2. M. Frederick Hawthorne, Broadening the Conflux of Boron and Carbon Chemistries," Proceedings of the Tenth International Conference on Boron Chemistry, Contemporary.
BOI-017 Chemistty, Edited by M. Davidson, A.K. Hughes, T.B. Marder, K. Wade, the Royal Society of Chemistry: Cambridge, 197 2000). JA-2 RU0410004 EVOLVING PATTERNS I BORON CLUSTER C11EMISTRY. A REASSESSMENT OF SOME OLD GENERALIZATIONS
Mark A. Fox and Ken Wade
Department of Chemistm Durham Univet-sitj, Science Laboratoi-ies, South Road, Dui-hanl D111 3LE, UK, e-niail: m. afioy Cuditt-hurn.ac. uk, kenneth. Wade Citchii-hUm.ac.uk
In the three decades since te structural patterns in boron custer chemistry were described in terms f near-spherical deltahedra or fragments thereof, [1] and rationalized in tcr-ms of the number of electrons available for skeletal bonding, 2 our knowledge of te area has increased very substantially, notably by the synthesis and Structural caracterization of very many new boranes ad heteroboranes, particularly carboranes. metallaboranes and metallacarboranes. Althouoh the main features of the original structural patterns have poved remarkably persistent, other features have emerged that dserve appraisal. This paper will summarize hat we now know about the structures of borancs and hetcroboranes and outline how they can now be rationalized. It will touch on sch isues as the ollowing: (a) the dentities of the parent deltahedra and scope for alterriatives; (b) fragmentation of deltahedra by vertex removal or ege cutting,
(c) skeletal atom dentities, orbitals, connectivities ad cectrone(yativ it IC S, (d) the influence of ligands. especially hydrogen, on skeletal shape, (e) frontier orbital considerations; (f) skeletal rearrangements: (g) fused polyhedral and, (h) echoes of the pattern elsewhere in cluster chernISILI'V.
1. R.E. Williams, Inot-a. Chem.. 10 2 0 1971); Adv. noi-. Chem. Radiochem.. 18 66 (1976). 2. K. Wade, J Chein. Soc., Chem. Commun., 792 197 l);.4(1v. Inora. Chem. Ra(liochcni., 18, 1 1976).
21 IB-2
RU0410005
NEW TYPES OF CARBORANES AND PHOSPHACARBORANES
Boliumil tibr
Institute oflnot-ganic Cheinisti-v, Acadenn q Sciences the Cech Rpublic, Rescai-ch Centre fioi- New Inoi-anic Con7pound ad Matei-ials, Unive -sitv f Paj-(h4bice, 250 68fe1near Pi-ague, Czech Republic, e-inail: stibi- iic.cas.cz
A simple ethod by Brellochs 1 made now the ai-achno-[6-CB,)H141 anion one of the ost ']able carboranes. ffi-h-vield snthetic methods startinc, frorn this anion ere develope to aval I':,
PS 2,1-PCBF 4-C88H14 2-CBrH7- H\ PPN' saft
2 C Et3N, EtN THF. HF -78-C t2N N2 -78'C (59', 02) -CB-,H, NR,' say Cs' salt 2. Et3N 220 T
,OX2 20 1 0 6-CE 014 d g PS P
1-CBqHj 6-CBqH12 1-CBHl,
6.1-PCE N isolate a series of essential rnonocarbaboranes I-CB7Hg_, 4-C138H14, I-CI381-112, I-C1391110-, and 6-CB,)I-l ,-, together with te two novel closo anions 4-CB8H9- and -')-CB(,H7-. Phosphorus-Insertion reactions with 4-CB8HI 4 and I-C13817112 gave phosphacarboranes closo-2 I - and 6 - PCB8Hq, respectively. Analogous reactions with
H 4,6- and 4,5-C2B7H]3 led to three somers of PS PC, deprotonation nido-P2C2137H9 and P-Insertion into 5,6- 0 D. CB8H,, and 6,9-CB8Hj0`- resulted in the
5.6-C 2 H 2 7,8,9-PC2BSH,, 7,8,9-PC2BH,,- formation of two isomeric II -vertex nido- PC-,BRH svstems. PC _ deprotonation R-7t__
PS C13
5 6-C2BH12 7,8,1 PC2B8H,, 7,8,1 1-PC2B8Hjcj- ,_ 7.8,9,10-P2CA7H9 ..WfYll H --able RT, 24h NEt, 4,5-C2B7HI3
Pci, 2 : %PCI,. RT, 12h 4.6-CA7H13 7.8.9,11-p2CA7HI 7.9,8.1(-P2C2B7Hg H, e-7,9,8,10-P3CB7H7
The work as supported by the Grant Agency of Academy of Sciences of the Czech Republic
(urantL o S4032007) and the Ministry of Educatlon of te Czech Republic project no. LNOOA028).
B.fireflochs In (_'o171en11)oraii, Bomn Chelnisv 7, K. Wade, M. G. Davidson, A. K Hughes and T. B. Marder, Eds, RSC, Cambridge 2000), 212-214.
22 IA-3 RU0410006
POLYBORANES. CARBORANESAND "ETEROBORANES
C.-J. Maier. A. Maier, P.Grelwe, M. Hofmann H Pritzkow, W. Siebert
Anorganisch-Chemisches Institut der Universitcit Heitlelberg, D-69120 Heitlelher-, Germain! e-maik i5a)iv.lirz.ut7i-heid-lber(-.de
Dehalogenations of the d1borane(4) derivatives I lead to the blue, folded cvclo-tetraborane 2 R NiPr2, and to the yellow tetrabora-tetrahedraiie 3 R = 2,2,6,6-tetramethylpiperldino (TMP) [I].
Attempts to synthesize a cyclo-pentaborane (B-R) from 1, R = NMe2 and Nle-,N-BC12 Yielded colorless 4 of the composition B6(NMe2)6 a constitutional isomer of the red cvc/o-hexaborane (13-
NMc2)6. Te X-ray structure analysis and calculations confiri-n te presence of planar bicvelo- tetraborane 4 R NMe2 2].
R R
B R R R B B R__ __-R R213 -- B --- B BR2 B B -B B B B V C I R \ R i R K R 1 R = NiPr2, NMe2, TMP 2, R = N'Pr2 3, R = TMP 4, R NMe2 New derivatives of the closo-C,13,, carboranes 5 were obtained from R'-C(BCI,) formed by hydroboration of borylalkynes wth IBCI,. In R2 = Ch te halo-en atoms mav be substitued by
AIMC3 or LIC--CCMe3 t '-Gave pentaorganyl drivatives 3 Dborontetrachloride reacts with CNC5-SiW3 to fo rm the neutral nido-carborane 6 [4]. Dehalogenation of cis- b1s(d1chloroboryl)hcxene-3 leads to 7 R = Et), confirmed by an Xray StrUCtUre analysis. The formation and structures of heterocarboranes 8 (X S. NMe wll be reported 5]. RI BC13 C1 2 R R R B R 2______R 2 Me,,,, e C ' C R 2 -B 2 x R Me Me e 4, R Rl" 13 2
i R R GI
5,R 1 CH2CMe3, R 2 C, 6 7 R = Et 8, X S, We
I.C.-J. A4aier, H. Pritzkow, W. Siebert'Angew. Chem. 1999, 111. 1772-1774. Int. Li EigL 38. 1666-1668.
2. A. 10aier, N1. Hofmann, H. PritzkoN, W. Siebert, Angew. ChL'1?1. 002, !14. 600-!602, hit E Egl. 1, 1529-
1532.
3. M. Biyer, 1. Pritzkow, W. Siebert, Eur.d. hiorg. Chein. 2002 i print.
4. P. Greiwe, A. BCtULIser, 1. Pritzkow, T. Kahler, P. Jutzi, W. Siebert, Eur J lnor'v. Chon. 2000, 19-7.
5. P. Greiwe, H. Pritzkoxv, W. Siebert, Eur.d. norg. Chem. 2001, 1599-1603.
23 H3-3 RU0410007 THE USE OF ORGANOBORON HALIDES IN ORGANIC SYNTHESIS
George W. Kabalka, Zlion-zhi Wu, ad Yuhong Ju
Department of Chemisoy, Te (niversio, of Tennessee Knoxville, TA39996-1600 USA, e-niaik kabalka zak.edu
Boron halides have been extensively used in oroanic chemistry. Simple boron trihalides are 'hzed for ether cleavaoc reactions. alogenation of aldehvdes, haloborat'on of alkynes, and enolization of carbony'l compounds. Or-anoboron halides have proven to be especially useful ir, Aldol chemistn! and in thl- area of stereochernicaliv controlled reductions. We have found that boron halide derivatives can be utilized to build molecular rameworks via te fcrTnation of carbon-carbon bonds. As an example, boron trichloride induces a reaction between aromatic adehydes and styrenes to produce 1-3-dihalo-1,3-diarylpropanes [1]. In addition, j1K\1boron dlialide ad dalkviboron alide derivatives react v6th aromatic adchydes in a Griunard-like fashion to enerate alcohols, alkyl halides and hydrocarbons depending on the reaction conditions utilized, as illustrated below 2].
0 014 14 R-)BC1 HO PI
More recently we discovered that the reactions were applicable to vinylboron halide derivatives. Dicne products were obtained as a result of multiple migrations of the vinyl Molety.
0 Br Br H BBr_j
The dcussion will provide and overview of te advantages of the use of boron halides in organic synthesis.
I Kabalka, G. W.-, Wu, Z.: Ju, Y. Torahedron Len- 2001, 42, 5793 Kahalka. G. "., Zhongzhi W, Yuhong, J. H Teirahedi-on 2001, 57, 1663.
24 CA-1 RU0410008 CLUSTER FLUXIONALITY AND REARRANGEMENT IN TEN-VERTEX CLOSO DCARBABORANE SYSTEMS
Daniel L. Ormsby, Robert Greatrex and John D. Kennedy
Department of Chemistty, University of Leeds, Leeds LS2 9T, UK; e-mail: R. Greatrex chem. leeds. ac.uk
Intracluster rearrangement in the twelve-vertex parent closo carbaborane, (' 131()H[2, has received much attention, but the ten-vertex QB8HjO systern has been neglected. It is well known that the kinetically most readily formed isomer 1,2-C2B8H,( will rearrange to a
MiXtUre of the 1,6- and 1,10- isomers when it is heated to 250 C, and thence to the 1,10- isomer exclusively at 350 C 1] A key to an understanding of the echanism of this process lies in a study o the isoelectronic metallacarbaborane system 2-((6MC6)-(-1oso-2,1,6- RuCB7H9 2,)]. This species exhibits an interenantiorneric fluxionality for which te precise exchange of particular sites Is well defined by NMR spectroscopy. This behaviour has been interpreted in terms of a double-d1arnond-square-diarnond (DDSD) echanism, involving isonido-type inten-nediates or transition states. We now report the use of DFT teory and frequency calculations to confirm the essence of this process in the model compound [2- (C61-l6)-2,1,6-RuC2B7H,)]. 5 5 q 9 2
' i O 0 6 3"
The Sccess of this technique has led us to apply the same procedure to te elucidation of the isomerism echanisms of the ten-vertex CBsfll,) somers. and ihe results will be dscussed.
1. F. N. Tebbe, P. M. Garrett, D. C. Young and M. F. Hawthoric, J. A. Chem. Soc., 1966, 88, 609 2 M Bown, T. Jelinck, B. tibr, S. Hei-mdnck, X. L. R. Fontaine. N. N. Greenwood, J. D. Kennedy and M. Thornton-Pett J Chem. Soc., Chein. ommun. 1988, 974 3 K. Nestor, M. Mun1hy, B. tibr, T. R. Spalding I X. L. R. ontaine, J. D. Knnedy nd M. Thornton-Pett, Collect. ('--ech. Chem. Commun. 1993, 58, 1555.
25 CB-1 RU0410009
SEARCH FOR INTERINIEDIATES IN TE CATALYTIC HYDROBORATION WITH QUINAP AND QUINAPO LIANDS Ilya D. Gridnev, Andrel Korostylev, and John M. Brown Dilson Perrins Laboratoq, Oxford nivei-sity, South Pal-kS Rd. X 3Y UK
Catalytic hydroboration has been actively studied for almost 1-0 years [1]. It is an attractive alternative to traditional livdi-oboration due to the milder conditions and controllable stereochemistry. However, no mechanistic studies in this field have been reported until now. Followinu the success of a RN QUINAP ]](,and (1) in te Rh-catalvzcd hvdroboration of Inylarenes L-1. e have recently prepared its P0 analoL QfNAPO 2) and tested its R-h-complex a a catalyst in catal-y-tic hydroboration.
N N 0- PPh, 'OP:- 0
2 Althou-h the Rh complexes of I and 2 both exhibit catalytic activity, the ee's of chiral alcohols obtained via catalytic hydroboration-oxidation are generally far higher for the Rh-QUINAP catalyst.
OH
1 CatBH, Rh-QUINAP (Rh-QUINAPO) J -Me 2. H OH 202, R R QUINAP upto97%ee QUINAPO up to 68%ee
To again an insight in the echanism of catalytic hydroboration and to understand the origin of dfference in stereoselectivities of hydroboration catalyzed by rhodium complexes of I and 2 we leave carried out a low-ternperature NMR search for ntermediates in these catalytic reactions.
Reactions of Rh-QUfNAP and Rh-QUfNAPO with catecholborane in THF-c at low tcnipcraftires ave various hydride complexes, which are the first known intermediates of catalytic asvi-i-imetric hvdroboration to be observed by NMR.
D.Mannig, H, Noth. 41wcii'. Clicin. 1985, 97 979.
2. 1 . Doucet. E. Fornandez. T. P. Layzell, J. M. Brown, Chern. Eur J. 1999, 5, 1320 E. Fernandez,
k. Maeda. M. vV. Hooper, J. M. Brown, Chem. Eur J. 2000 6 840, K. Maeda. J. M. Brown,
Chein. Coniniun. 2002 3 . 26 CA-2 RU041 001 0 PROGRESS IN THE CHEMISTRY OF FIGHT AND NINE-VERTEX MONOCARBABORANE ANIONS
T. Jelinek', B. Stibr", J. D. ennedv6 and A Franken
'Institute ofInorganic Chemistn,, Academv ofSciences of the Czech Republic, Rc.scarch Centrefor New Iorganic Compounds nd Materials, Universitv o Pardubice, 250 68Pc,: near Prague, Czech Republic, e-maik jelinek( iic. cas.cZ bSchool of Cheinisoy, University of Leeds, Leeds LS2 9T Egland.E-mail: johnk(auchemistry.lecds.ac. uk
Brellochs I as reported recently a simple method of carbon nsertion into decaborane I 0 to produce effectively a series of 10-vertex monocarbaborane compounds, for example the arachno-[6-C1391-1141 (1) anion. This reaction opened the chance for scrutinizing te chemistry this species in more detail. Anion I on heating under Vacuum gave te long anticipated 9-vertex closo monocarbaborane anion, [4-CBsH,)]_ (11) wich was obtained in a yield of 45% to-ether with a small quantity of other compounds. This thermolysis was workinc, also in the case of C-substituted species to prepare the corresponding anions [4-CH3- 4-CB8Hs]- (111) and [4-Ph-4-CH8]_ (IV). Anions II-IV were characterized by NNMR spectroscopy and an X-ray diffraction analysis. Anion reacted with lemental iodine to isolate one dlodo ad two monolododerivatives, namely [5-1-4-CB, Hj (Nla), [2-1-4-C13JI81- (Vb), and [5,6-I,-4-CBsH8] (Vc). Brelloclis also reported the existence of a new 0vertex closo monocarbaborane isomer, [2-CB9Hjj (VI), which is the second known representative of the closo monocarbaborane famliv. Hato2enatio of ;_Ic compound V with N-brornosuccinimide gave d ffe re t mono-, di-, and 'bromoder'vateves NANch. after heating rearranged into the classical 10-vertex c1oso-[1-CB,1)Hjj species. The Br- substituted derivatives prepared in this manner are not aval']able b-v direct halogenation of the closo- I C B, H anion, which is verv mportant for studying catalytic activities of hose mpouriGs.
The work was spported by the UK DTI and the UK EPSRC (grants nos L49505 mega M83360), and the Nfinistry of Education of the Czech Republic (project no. LN00A028).
L B.Brellochs In Contemporaty Boron Cheinistry, K.Wadc, M. G. Davidson, A. K. Hughes and T. B. Marder, Eds, RSC, Cambridge 2000), 212-214.
27 CB-2 RU0410011 NOVEL APPLICATIONS OF PERFLUORINATED ARYLBORON CkTALYSTS IN ORGANIC SYNTHESIS
Vladimir Gevor-yan
U"niversiti, of Illinois al Chicago, cmail.- vlad ,uic.edu
We found tat B(C6F5)3.can serve as a very efficient catalyst for important orLanictransformations such as C-0 and -C bond cleava-e and forrnin- reactions. It as found that rrimarv alcohols ad ters can be effectively reduced to the corresponding hdrocarbons y 11SID3 in the presence of cataIrtic amounts of B(C6F5)3 To the best of our knowled-e. this is the first example of catalytic ue of Lewis acid in the reductio o alcohols and others with hdrosilanes. h ws found that secondarv and tertiary alcohols, as ell as the tertiarv alkv] ethers. did not react with HSiEt3/(B(C6F5)') reducing reauent at all The followin- relative reactivitv order of substrates was found: primary >> secondaril > tertiary A plausible mechanism for this non-traditional Lewis acid catalyzed reaction is proposed. Extension of tis methodoloia-v to the reduction of carbonyl group has proven te 2cneralitv of this m0thod Tus. te aliphatic carboxyliC LIFOUP as fficiently reduced to the methyl group by fSIEt' in te presence of atalyti aounts of BC6F5)3. Tis is thefirst exampic o a (hrect exhaustive reduction ol a)hatic carboxulic inction! Aliphatic aldehvdes, ac,,Ichlorides, anhydrides and esters also underwent complete reduction Linder 'lar reaction conditions. Aromatic carboxylic acids, as ell as other carbonyl fnctional equivalents. underwent sooth partial reduction to the corresponding TES-protected benzylic alcohols. It , as also found that B(C6F5)') can efficiently catalyze the allylation of secondary benzylic alcohol derivatives with aylsilanes. Various secondary benzylic acetates smoothly Underwent the allylation reaction under mild conditions to give te corresponding, allylation products in very high vields. Initial experiments on functional aroup tolerance demonstrated that bromo, acetoxy and benzyloxy groups re tolerated under these reaction conditions. Finally. we have developed a convenient and highly efficient method for the B(C6F-',)3- catalyzed trans-selective hydrosilylation of alkenes. The mechanism of this ovel protocol operates via direct addition of slicenium type species across C=C bond followed by trappin- of te resultant carbenjurn ion wth boron-bound hydride A number of diversely substituted slancs possessing both aryl and alkyl groups t te silicon atom were efficiently prepared usimi this hydrosilylation methodolo-y. The possibility to employ aryl-containing livdrosilancs in his reaction oens broad capabilities for the synthesis of alcohols i a trans-
sclectixe hydro , Iv I at on/Tamao-FIcnimL, oxidation sequences complementary to the xisting (i. slective h,idroborationoxidation protocol.
28 IA4 RU0410012 INTRAMOLECULAR AND SUPRAMOLECULAR CLUSTER INTEIUXCTIONS
Jonathan Bould, Andreas tranken I md Jelinek, John D. Kennedy, Colin A. Klner,
Michael G. S. Londesborough, and Mark Thorriton-Pett
Departmentof Chemistry, UniversityI of Leeds, Leeds UK LS2 WT Norther Egland, EU,
e-rnail:johizk(o j'cheni.leeds.ac.uk
Boron-containing custer chemistry has s far largely developed in terms of a molecular chemistry based on single clusters. A more extensive molecular chemistry becomes available when the clusters are lked covalently. The extreme of covalent linking is intimate cluster fusion to engender 'big boron' macropolyhedral species. A complementary extensive chemistry can arise from non-covalent attractions nvolving cluster compounds, for example cluster molecules with large surfaces, or with irregular surfaces that may dovetail, or with other mutually attractive features. In principle there will be a continuum of behaviour between the covalent and non-covalent extremes. Traditional single-cluster:D polyhedral boron chemistry will therefore be considerably extended not only by the intimate covalent parablosis of clusters to produce big molecular species, but also by molecule-molecule interactions to generate novel supramolecular formations.
29 IB-4 RU0410013
NENVASYNIMETRIC SYNTHESES WITH 10RONIC ESTERS AND FLUOROBORANES
Donald S. Matteson
[J'ashin-lonState Unhersitv, Pullman, If/A 99164-4630 U.S.A. e-mail: dinatteson wsu.edu
1-loinolouation of boronic esters of chiral dols 71th LCHC1, provides a broadly useful, highly stereosejective insertion of stereogenic centers [1]. The conditions for conversion of arviboronic acids to aryltrifluoroborates by potassium bfluorlde reported by Vedejs and
coworkers 2 have been found surprisingly4-- applicable to sterically hindered asymmetric alkvlboronic esters. Even the particularly resistant pinanediol esters are rapidly cleaved to 70% free pinanediol and alkyltrifluoroborate at equilibrium under the usual reaction conditions. The alkyltrifluoroborates Ith silicon tetrachloride rapidly fori-n. alk-,Idlfluoroboranes wich react with functionality such as azide tat is inert to boronic esters. We ha e applied tis nc cemistry to te preparation of asymmetric pyrrolidines such as 1. 98' 'o e measured 3 Ts chemistry, is providing a broadIV useful route to chiral secondary entities. and slio s promise for oher applications. - Br /- N Ph -B 3 1. LiCHC12 2. PhMgBr CY Cy N3 Cy CY
KHF Ph SiC14 Ph -N' Ph H20 IO BF3K Ph N MeOH N3 250C BF2 N3 BF2 H
1. Reviews: Matteson, D. S. Tetl-ahedl-on 1998, 54, 10555-10607; Matteson, D. S. J 01-ganomet. Chem. 1999, 581, 51-65. Vede's, E.: Chapman, R. W.: Fields, S. C.: Lin, S.; Schrimpf, M. R., "Conversion of Arviboronic Acids into Potassium AvItrifluoroborates: Convenient Precursors of Ar lhoron Difluoride ewis Acids",J. Org. Chem. 1995, 60, 3020-3027. 3. Matteson. 1). S..- irn. G. Y, manuscript submitted for publication.
30 CA-3 2111111011[1111[ RU0410014
REACTIVITYOF THE CLUSTER CORE OF RUTHENABORANES TOWARD PHOSPHORUS COMPOUNDS
Mamoru Shirnoi, Lourdes N. Pangan, and Yasuro Kawano Department of Basic Science, Graduate School of Arts and Sciences, University of Tokyo, Meguro-ku, Tokyo 153-890-, Japan cshimoi niail.ecc.ii-toA ,o.ac.jp
diruthenaborane nido-[ICp*Ru([t-H)I B3H71 (1) undergoes cluster degradation thl-01.1-11 the
f zn Z: action of phosphines to give [CP*2RU)(PI-I'3)( L-H)(BH ) 3 PR3 = PMe3, PN!e Ph, PHPh,) and BH3-PR3. The reaction of I with less basic phosphates causes cluster rearrangement to produce iiido-[I-OR-2,3-(Cp*Ru)2tp-P(OR)2fB3H5I 4, R = Me, Ph). During the course of further study, we found that the initial product of the reaction between I and phosphorus donors was an arachno-diruthenapentaborane [Cp*,Ruj t-I'l)(PR3)BA ] 2). This species is regarded as a common intermediate for the aforementioned reactions. Cluster.' was observed in te NMR spectra of the reaction mxture of and Pl-lPh, or P(OPh)3. Rather low basicity and bulkiness of these phosphorus compounds retard the conversion from 2 to te 'Thai product, 3 or 4 Atempts to isolate 2 ws tinsuccesful because it readily reverted to .
Ru PR3 RU Ru 5 R B R3P NW/ 2 PR3 phosphres PR3 phcrsphftes
-eH3'PR3 -H2 OR
BX Ru Ru Ruj x fi I --- ' - B RO-P- Ru-,/ PR3 I RO 3 4
An arachno-ruthenapentaborane [(q 6-C6Me6)RUl34Hj(] 5) reacts with PMC3 to afford 6_ C6`Me6)Ru(PNIe3)B3l-171 6) and B143'PMC3.
e3 Ru B P M Ve3P 11 - --I -BH-3-PMe3 B-0 B"WI B B 4( \0 \0 5 6 31 CB-3 RU0410015 SYNT14ESIS AND BIOLOGICAL EVALUATION OF BORON CONTAINING EGFR PROTEIN TYRr)SINE KINASE NHIBITORS
Hiroyuki Nakamura, Toru Asano, tMio Goda, Hiroshi Yamamoto, and Yoshinori Yaniarnotot
Depai-onent of Chetnisti-i,, Facultv o Science, Gakushuin Univei-siti; Toshima-kil, Tok-vo 171-8588, e-nzail: hit-ovitki.nakainui-a Cd gakushuin.acjp I - "Depai-tment of Cheniisti ,, Gi-aduate School of Science, Tohoku Univel-sitj,, Sendai 980-8578, Japan
The protein tyrosine knases (PTKs) play critical roles in many of the signal transduction processes t hat control cell growth, differentiation, mitosis, and death. Therefore PTKs are important targets for te development of therapeutic agents for the treatment of diseases such as cancer and psoriasis. Lavendustin A 1] is oe of the natural product inhibitors of the eidennal arowth factor receptor (EGFR) PTK and consists of two benzylic parts in conjunction with a
sallevlate rinc, vla an amine. The active pharmacophore of Lavendustin A has been shown to consist of the more smplified benzylarnine 1. We focused on the OH ad COOH groups of the molecules and designed the boron containing EGFR-PTK nhibitors by the replacement the OH andior COOH group with a boric acid group.
We first snthesized the boron containing mimics 4 of the Lavendustin A active
pharmacophore I from various arillines 2 and aldehydes 3 by the reductive amation 2.
Furthermore tertiarv amines 5 have also synthesized from 4 with aldehydes by the ductive
animation or benzylic halides by SN2 reaction. The biological activities of those boron containing
amines and will be discussed.
HO
HO aOH
NH
COH Lavendustin A Lavendustin A active pharmacophore
RI
NH, OHC reductive > animation X R" + NH R 'OR I R 2 3 4 5 'R 1. Onoda. T.: Inunia. H.,- Sasaki Y Hamada, M.; ssh1k], K.,- Naganawa, H.; Takeguchl T J Nat. 1'1-()d. 1989,52. 1252. 2. Mu. F.: Coffin-. S. L.: Resc 11, D. J.; Cicahlen, R. L.; Verdler-Pinard, P.; Hamel, E.; Johnson, J.; Cushman, M.J. Med. Chem, 2001, 44, 441.
32 CA-4 RU0410016 LUMINESCENCE OF GROUP 4 METAL CARBORANE COMPLEXES
Hyosook Jang. Chang Hwan Shin, BVLIM-1 Un Jung, Sac Chac Jcoun(4' Young-Kyu Han 2 ,Eunkee Flong, Younggyu Han, Hong -Ku Shim ad Y0-un!Yk'YL Do
Department of Chemistrv, SMS-BK2 ad CMDS, KIST DacJeon 305-701, Korea Spectroscopy Laboratoi y, RISS, Daejeon305-600, Korea
2Analytical and ComputationalScience Center LG Chemical, Daejeon 305-380, Korea e-mail: ykdo CLkaist.ac. -r; hap.-Ilsms.kaist. ac.krl-Ykdo
The iportance of luminescent functional materials is ncreasing in various opto-clectronic fields. Especially organic electroluminescent (EL) materials have been widely studied sce the discovery of tris(8-qu1no1inato)a1urmnL1m as an emitting material by Tang et al [1]. To synthesize new luminescent materials, we have employed isopropyl-bridged cyclopentadlenyl o-carboran I igand to synthesize dissymmetric and asymmetric group 4 metal complexes. The measurement of the rilechano-, photo-, and electroluminescence revealed that these complexes constitute the first examples were the use of carborane clusters in developing Urnincscent functional aterials has been successfully demonstrated. When mechanoluminescence was measured by applying pressure to the sngle crystalline samples of the dssymmetric M(rl :Tj1-CPCMC2CBjj110C)2 M T1, ad Fit) in non- centrosymmetric space group and the asymmetric ZrCp*Cl(lil :il'-CpC\,Ic-,C'B,(,Hl )C) in centrosyrnmetric space roup, only the dissymmetric Zr and Hf complexes ave sL'Ilals in the tme- integrated emitting spectrum. The EL properties were measured by incorporating te smples into a hole-transporting polymer of poly(N-vinvicarbazole'). Diss,,illmetric Hq and asymmetric ZrCp*Cl(q i:Tj1-CpCMeCBjjHj(,C) showed zeen EL while dssymmetric Zr(Tj5:-q'-CpCMeCBj0H1(C)2 ave ellow EL. In order to uderstand the nature o hoto- and electroluminescence of the fore(oing, sstems, the molecular energy levels of dssymmetric
M(115:q '-CpCMeCBjoHjo0 a the Z ground state a we'll s at the excited state were Calculated. 'ou 4 metal carborane complexes reported in tis presentation constitute not only the of inechanoluminescent organornetalfic systems bt also the first examples of efectrolurninescent carborane complexes. Dtailed accounts of the chemistry associated with the systerns, whose preliminary results have been communicated 2], will be presented.
[I] Tan(,, C. W.; anSlyke, S. A. Appl. Ph,,s. Lett. 1987, 51, 913. [2] Hong, E.; Jail-, H.; Kim, Y.; Jeoung, S. C.; Do, Y.Adv. zVater 2001. 3, 1094.
33 CB4 RU0410017 (S)-(+)- AND (R)-(-)-2-ME-rliYL-1-BORAADANIANTANES
V. A. Ponornarey', M. E. Gurskil', D.G. Pershin', K. A. Lyssenko b M. Yu. Antipin b Yu. N. BubnoVb
"A'. D. Zelinskv Institute ?f 01-1ganic Chemisti-)- Rssian Acadenzj qfSciences, 119991, GSP-1, Lcninskipi-osp., 47, Moscow, Russi, e-mail: boi- caci-.ioc.ac.ru -anov Instimic OfOi- noclement Compounds, Russian Academj, of Sciences, 4.N. Nesmc.i 1 !Ia
11 9991, Favilova sti-., 24, Moscow, Russia.
Both the (S)-(_)-Ab, 96% de) and (R)-(-)-2-metlivi-l-boraadamantane (le. 90% de)
compounds ere solated b crystallization othe corresponding phenylethylamine adducts (1)
fi-om hexane.
(-i-)R THF _ -Ph PI) Me B B Me H B Me -.W- %H_ NH,
I R crvslalh Crvstallizaion
Hexan' 7aio" Hexane -4- (+)-R
Me B Meij, B B___,,ojMe B Me lass + More More + LZ% soluble) soluble Soluble)
(+ le (+)-Id (+ la (+)-lb B F3'E 20 BF, EtO -rHF THF THF y Py T F
Me B Me B B Me B Me
-PI 20 -3, ['121) 35.6- (S) -2 (R) 2 (R)-3, [a]D 33.11 (S)
In all cases the diastereomeric excess was detemilned by 13C NMR. The absolute
C011FI(TUration of' (-)-lb was established by Xray analysis. The air-stable ciral pyridine
addLICtS (S)-(+)-3 and (R)-(-)-3 ere synthesized b t action of'pyridine on the cral
tctr ihvdroturanc complexes -- 2 and +2.
This work was supported by RFBR (Grants 01 03-32465, 00-15-97378, 02-03-311-248).
34 IA-5 RU0410018
RECEN'rADVANCES IN THE CHEMISTRY OF CARBORANES AND METALLACARBORANES
Narayan S. Hosmane
Departnientof Chenzistry and Biochemistry, Northcrn Illinois UniversitY, DeKalb, Illinois 60115, USA, e-niail: nhosmanegnhi.edu
We ae been actively involved in the study of half-sandwich and full-sandwich metallacarboranes of the C2B10- C2B9- and C2B4-cage systems with constrained geometries (Figure 1) in which the heteroatom, E = 0, N or P, of the anionic C(cage)-appended molety is cy- bonded to the metal that is also completed with the open C2133-face of the carborane igand in an il5-fashion. The preliminary results of this research have been reported very recently 1,21. When the cosahedral carboranes containing the ansa-11-ands are subjected to decapitation reactions in the presence of ethanolic KOH, the resulting species are the open-cage inonoanion [nido-(R)CBqH1i]- in which the appended molety remains intact. Further deprotoriation results in the formation of the corresponding trianions as shown below. The reactivity of these 11gands and those of the C134-carborane systems toward a number of main group ad early transition metals will be presented in detail. In addition. novel synthetic routes to 'OB-enriched pentaboranc(9), decaborane(14), and iso-131, I-122 will be pesented.
ye H Me U+K+ 0- Lj + C -OH 2 n-BuLi KOH K+ THF, -780C Me EtOH 2 n-BuH
Maw M Si, Ge M TW, 7 - KCII
H2L, )V[-Me
Figure 1. Synthesis of Group 14 Metallacarboranes of Constrained-Geornetries
1. Zhu, Y.; Vyakaranain. K.; Maguire, J. A.: Quintana, W.; Te1xider, F.-, Vifias, C.; Hosmane,
N.S., Inoig. Chein. Cninnin., 2001, , 486-489. 2. Zhu, Y.; Maguire, J. A.; Hosmane, N. S., Inov- Chein. Coninnin. 202, 5, 296-299.
35 IB-5 RU0410019 ENOLBORATION OF CONJUGATED KETONES, SYNTHESIS OF BRIONIC ACIDS, AND P-AMINO ALCOHOLS
Marek Zaidiewicz, Wojelech Sok6l, Joanna Cytarska, Agnieszka Tafelska-Kaczmarek, Andrzej Wolan, Adam Dzielefidziak, and Adrzej Prewysz-Kwinto
Faculty of Chenjisti),, Mcolaus Copernicus University, 87-1 00 Toriai, Poland e-inail: zaid1evi chcm.uni.torun.pl
Enolboration of cvclohex-2-enone (1). 3-i-netyl- 2), 3.5-dimethyl 3 3,5,5-trimethyl- 4), and ' .4.,-',.5-tetramethvlcvclohex-'-I-eiione (5) with chiorodievclohexviborane and LDA was Studied I]. The reaction with chlorodicyclohexylborane proceeds by deprotonation at the 6- position. Aldolization of the dienolborinates wth benzaldehyde and acetyaldehyde provides the corresponding anti aldols with 87-95 slectivity. Ketones 4 and undergo competitive deprotonation at te 3-i-nethyl roup, and aldolization at the 2-position leads to the Baylis- Hillman tpe of product. Lithium denolates obtained from te less hindered 13 react with benzaldehNde and acetylaldehyde producing preferentially anti a1dols. owever, svn selectivity predominates for te denolates derived frorn the ore hndered4 and . The synthesis of boronated x-amino acids with a quaternary center at the a-position, for BNCT therapy, has been studied. Approaches to the synthesis of a-methyl(2-methoxy-5- d1hydroxyboryl)phenylalanine, and a cyclobutyl analog of BPA, will be discussed. Te d1hydroxyboryl moiety was introduced either in a classical way by metalation-transmetalation or by the cross-coupling reaction in an ionic liquid leading to higher yields in a shorter time 2]. A convenient synthesis of 3-acylbenzofurans and other 3-substituted derivatives, has been developed [3]. Enantioselective reduction of alkyl substituted 2- and 3- acetylberizofurans with dilsopinocampheyl chloride proceeds to give the corresponding alcohols of 80-95 ee. Their configuration was established by X-ray analysis of p- nitrobenzoates. Aryl benzofuryl ketones are not reduced. The reaction was used as a key step in the enantioselective synthesis of 2-(l -bydroxy-2-propylaminoetliyl)-3-(2- phenylethyllftrizofuran a propaphenone analog with antiarrhythrme activity.
1. M. Zaidlewicz, W. Sok6l, Tetrahedron Lett.. 2002, in press. 2. M. Zaidiewicz. A. Wolan J. Or,,anotnei. Chem., 2002, in press. 3. M. Zaidlewicz, A. C'hechlowsk t, A. Prcwysz-KNv1n1o, and A. W 'tczakHeterocvCles, 2001,55,569.
36 CA-5 RU0410020 closo-IRIDACARBORAN'ES WITH CARBOCYCLIC LGANDS:A NEW NE-PoT .SYNTHETIC PROCEDURE
Alexander V. Safronov,-Tatyana V. Zinevich, Fedor M. Dolgushln, Pavel V. Petrovskil" Evgenii V. Vorontsov and luor T. Chizhevsky
AA Nesmeyanov Institute of Organoelement Compounds, 28 Vavilov Sir.,
119991 Moscow, Russia, e-mail: alsaphg ineos.ac.ru
In an attempt to extend the range of nown 12-vertex rdacarboranes of the closo- (L)IrC21391-111 type (L - cycloolefin-based ligands) and to further develop their chermstry an I efficient synthetic procedure has been introduced. It involves the treatment of zido-7-R-8-R -
718-C2Bq1-ljo]_K R R=H, Alk, ArAlk) with drneric p-halide complexes [1,5-R 2 COD)MCI]2 R 2=H, Me) in C6H6/EtOH mixture at room temperature to form a series of
mono ad polynuclear closo-iridacarboranes containin T 1.2- q 3_ cycloc-nyl ad'/or cyq .1
q2,3 _cyclooctadienyl-type 11gands at the metal vertex. The potential versatility of the present approach is demonstrated by the following scheme:
H RI Ir
R R K- tiTj'-l.5-R2,-C01))IrC1j, R CI ,
R R= Ne R. R=o-(C1l,)-C.1I., H-C cull [1,C CH,
GI,
The solid state structures of some of te products as well as dynamic behavior of fluxional complexes 'Have been studied in details by a combination of X-ray diffraction and niultinuclear low temperature NMR methods. This work was supported by the Russian Founda'lon for Bqslc Research Grant No 00-03-32-824).
37 CB-5 A1111110111 RU0410021
SULPHUR INTRODUCTION INTO B2H12 2- BY (NI12)2CS12CI2 - A NEW IIALOGEN-LIKEELECTROPHILIC AGENT
Victor A. Brattsev John H. Morris , Galina N. Danjlova c
'GNHCh TEOS, 38 Shosse E7701--iastov, 11 123 Moscow Russia, e-maik (ivbraginaik.ru; Sti-athclrde Univ., Glasgow, UK, e-111ai1j.11. morris straih.ac. uk 'Inst. Biophvsics, Dialned, Moscow, Russia
Earlier [I. 2 Nve found a way of ntroducing a sulphur substituent into BH]2 2- wit tiourea usin- te conditions of electrochemical oxidation. It resulted in te forrnation of [B:,H jSC(-H2)21 () and its structure was determined bv R and NNIR spectroscopy, X-ray ensialloL),Fap)iN,.andbvalkalinehvdrolvs1sinBl2HISH 2- with (NCS), vh ch as halogen-like characteristics. we studied the possibility of By ariaiog I I I I I I I preparing a dimer t tourea cation. [(HN),CS-SC(NH, )'12 and nstigated it as an 2- -lCI electrophilic agent, capable of ntroducing an S-substituent into 131217112 .In aqueous I solution. thiourea readily reacts with bromine with the formation of [(HN)2CS12 : This precipitates as te crystalline compound [(HN)2CS12CI (1).
2 (H-)N)2CS + Br2- [(HN)2CS]21 2 Br-
As it has been anticipated, the prepared electrophilic reagentz:1 1, on interaction with closo- dodecahvdrododecaborate danion, Bi 2H 12 2- ,leads to substitution of a proton wth the foliation of te compound I with a 3--S-bond:
2. NH2 S- + 2 + NH2 + (H,,N)2CS12 +(NH,)CS H+
B,(,H and CB H react with It under smilar conditions forming the corresponding inner thiLironlurn salts [BI(HgSC(NH:),]- and CB, H, SC(NH2)2, that after alkaline hydrolysis yield corresponding mercapto derivatives. In preliminary studies it has been found that this reagent 11 can react with N-acetanilide yielding o- and p-substituted derivatives:
CH3CONH-,, + (H2N)CS)2 2------ICH3CONH SC(NH2)21+
Malelc acid reacts wth 11 with the addition of HN)2CS12 2+ to the double bond:
HOCO COOH + OCOCH CHCOOH 2+ + (H2N)2CSI--'-
H H SC(N V12)2 SC(NH2)2
All thluronjurn salts prepare tis way yield correspondina mercapto derivatives after alkaline hydrolysis.
V. Brattsev, J.Morris. Proc. IM EBORON-9 I cidclberg, 1996, p. 67 V.Brattscv, J.Morris, Adv. in NCT, v.11, p.51-55, Elsevier, 997
38 CA-6 RU0410022
NEW FUNCTIONALIZED COBALTA BSMICARBOLLIDE)(I-) IONS
B. Gruner', J. PescV, J. Baca', 1. C'sarovaI h J. F. Dozol' P Seluckv d -I Ral.1)'
cl Institute of Inorganic Chemistry, 250 68 Pe2 near Prague, Czech Republic-, e-Inail.- gg tner iic ca. .cz,-6D-p(irtmentofllzorgunicClietiii. ti-voftheCliarlesUnivei-.5itvHlcivovcl2O3O, 120 00 Prague 2 Czech Rpublic; c CEA CadaracheDEDISE PILCD, 3108 St. Pul les Durance,
France; dNuclear Research Institute p1c., 25068 Re 7, Czech Republic.
Pr(.-sented are recent advances in the chemistry of selective extraction ayents (SEA) based on the cobalta bis(dicarbollide) anion [1,2-C2B9Hl 1)2-3-Co]- (1) used for treatment of nuclear quid wastes. Principally novel generation of SEA emerged from the idea of combining I wth groups capable of complexing tightly the Sr + and M3+ cations. Several new preparative methods were developed for introducing (-- xo-skelelal substituents into Bg) (or Bps.) positions in 1. An extensive screening study was performed to optimise the selection of metal figating groups. Also the mode of the selective moiety attachment was modified, using bonding via ethylene -Ivcol spacer ,2 or mono or M atomic bridge manner [2,3]. The range of the tsted metal seqUCstennL YUps comprises: phenols [1], crown ethers 2 phosphonic and phosphoric acid oieties 1,31. bdentate am'des, ad CMPO-like functionalities 4 CMPO= diphenyl Nalkyl carbarnovi-inethyl) phosphine oxide). Several new SEA proved being effective in transferring te target FadiOnLIC11CICS from IM HN01 into aromatic solvents without other additive the best -'- extraction fficiency bein- observed for CMPO substitution. Dscussed will be significant X-ra% determined structural parameters of the new anionic li-ands and their metal complexes, especia1v those of the CMPO series. These features, alon(2 with other xperimental evidence. account for the cation transl I ,r a a consequence of hdrophobic and charge compensated supramoiccular prticle for-mation.
The study as partly supported by the Grant Agency of Czech Republic (Grant No. 3/00/1042) and Ministery of Education of te Czech Republic (Pro'ectJ N00A028).
I J. Plesek, B.Gruner, S. Her-manck, J. Baca, V. Marecek, J. Janchenova, A. Lhotskv. K. Holub P.
Selucky, J. Rais, 1. Csarova, J. Caslavsky, Polyhedron, 21, 975-986 002).
2. B. Gniner, J. Plesek, J. Bca, J. F. Dozol, V. Larnare, 1. Csarovd, M. Belohradsky. J. Caslavskv,
New J. Cem. 2002), in press.
3. J. Plesek, B. GrUner, 1. Csarova, J. Baca, P. Selucky, J. Rais, J. rLariornet. Chem. 2002) in press.
4. B. GrUner, J. Plesek, J. Baca, 1. Csarov , C.Vinas, J. F. Dozol, V. Larnare, P. Seluck , J. Rais.,
New J. Chem., accepted. 39 CB-6 RU0410023 RAD10HALOGENATED POLYHEDRAL BORON CLUSTERS FOR I-ISE IN TARGETED ONCOLOGICAL NUCLIDETHERAPY
Stefan Si6ber I and Vladimir Toli-nachev 1.2
Deparmicin of'Organic Chemisirv, Institute of Chemisti-y, Uppsala University, P.O. Box i3l.S-751 2 Qwsala, Sive(len, e-mail: stefaii.sjobet-gEt,"kellli.uli.se
Di1TNi0)7 1'BiOMC(flcal Radiation Sciences, Box 535, S-751 2. L qpsala Universitj,, Uppsala, Siveden
Vhoui half o' all ]laid turnours can successfully be treated b surgery and external
rdcl!01110111p . IF, nam of t oer cases te 1aliure is caused bv te spreadin- of the turnour. The extent of the spread is often difficult to establish since dissirninated single tumour cells and \crN small metastases cannot be damosed. Chemotherapy with cytostatic drugs can sometimes hC11)). but there is a rcat need to dvelop other treatment odalities. TLirLnA oncological rdionuclide terapy is oe such method. Among radionuclides of 1111cre'l- r radlolialogens. which dspla a ariety of decav schemes, allowing a wide
range ot'applications i te field of nuclear medicine. Te selection of the radlohalogen is uo%erned \ the interided bomedical application ad by the "time window" required. Som of
the ost importam halogen nuclides in tis context are: I-)5 1 (Tif = 60 days, 100 electron
Capture (LC)). 1 '111TI,- 8 days. ), 123, (T,,, 13.3 h, 100 EC), 2 Tji 42 days, 23
7 % fi-), "By j ,2 16.2 h, 54 % 46',o EC), "Br (TI/2 = 57 li, EC), Br (T,; = 4 h, IT), I + Br (T h, B - (T /2= I I m n, and "' At (T 2 = 8 h, 2- -CBIIH,2-, nido-C2139H12- Some polyhedral bron clusters (closo-B,,H12,clo.yo and
clo.w-C,13 I'll 12) ave large potential as radiolialogen carriers. We have recently reviewer] our own and other ork in tis area [1]. In this presentation we will rport on the recent progress
ill Our laboratories.
The author thanks INTAS 99-00806), the Swedish Cancer Foundation and the Royal
Swedish Academy of Sciences for financial support.
i V Tolmachev and S. Sj6berp. Polyhedral Boron Compounds as Potential Linkers for
,Aitachnictil ol Radjohalo,-,clis o Targeting Proteins and Peptides. Accepted for publication
in Colicct. Ccch. hem. Commun- 2002.
40 [A-6 RU0410024 SUPR.A.ICOSAHEDRAL (METALLA)CARBORANES
Alan S. F. Boyd, Anthony Burke, David Ellis, Daniel Ferrer, Barry T. Giles,
Miguel A. Laguna, Ruaraldh McIntosh, Stuart A. Macgregor, Daniel L. OrmsbY. Georgina M. Rosair. Frank Schmidt, Nell M. M. Wilson and Ala J Welch
Heriot-Watt University, dinburgh E1114 4AS, UK, e-mail.- aj.welch Lt hwac.ilk tImperial College, London SW7 2AZ UK
Although supraicosahedral heterocarboranes have been known for many years tile area is still underdeveloped relative to icosahedral and sub-icosahedral analogues. Thus there are only a few tens of examples of closed 13-vertex compounds, and only three 3 examples of closed 14- vertex compounds, in the available literature. Most studied are 13-vertex metallacarboranes, MCAO. Only relatively few of the several possible isomers of these species have been described, and there is very little known about their flUXionality and isomerisation. We will describe several new 13-vertex transition metal metallacarboranes wth particular reference to teir structures and, in some cases, partial degradation.[I] We will also describe the first supi-alcosahedral pblock metallacarboranes.[2] Computational and VT NMR studies on these compounds have yielded confin-nation of 1-lawthor-ne's duble d-s-d- echanism for fluxionality of te 4,1.6-MC2Bo isomers and. for the first time, activation ener6es for tile process. Finally we will describe how these studies relate to recent progress towards derivatives of the elusive closed SLIpraicosahedral carborane C2B, HI-,. We thank the EPSRC. the Leverhulme Trust. The Carne ne Trust, The Nuffield Foundation and the Royal Society for support.
1. A. Burke et l, Collect. Cech. Chem. Conitrun., in press. M. A. Laguna et al. norg. Chim. Acta, in press. D. Ferrer et al, unpublished work. F. Schmidt et al, unpublished work. 2. N. M. M. Wilson ct al, Chem. Commun., 2002, 464.
41 I B-6 11 I 1 11 I I 1 1 11 1 1 1 RU0410025
SYNTHESES OF BIOLOGICALLY ACTIVE MOLECULES VIA
ORGANOBORANES
P. Vecraraghavn Rarnachandran
Herbert C. Brown Centerfor Borane Research Departnient of'Cheinistry, Purdue University JEest Lafq-,-ette, IN 4 7907-1393 e-inall: chandran0a'PU7-due.edu
AlIvIboration was discovered by Mikhailov and Bubnov four decades ago. Two
decades later, Hoffmann and coworkers introduced an asymmetric version of tis reaction.
Since then several chiral auxiliaries have been utilized to ahieve h,h enantioselectivity in
allylborations. rown and coworkers introduced .-Pinene as a successful chiral auxiliary for
allvl- and crotviborations. We have utilized this reaction, in combination with Grubbs' ring-
closing metathesis reaction for the syntheses of a variety of' biologically active olecules,
inClUding tubulin-polymerizing anti-cancer agent, epothilones. Some of our recent target
molecules and their syntheses will be discussed.
42 CA-7 RU0410026
BORYL COMPLEXES AND CATIONIC BORANE ir COMPLEXES F MANGANESE: HETEROLYTIC CLEAVAGE OF THE IVIETAL-COORDINATED BUI a BOND
YaSUro Kawano, Takahiro Yasue, and Mamoru Shimol
Department of Basic Science, GraduateSchool of'Arts and ciences, University of Tokyo, Meguro-ku, Tokyo 153-8902, Japan ykawano )jcom.home.ne.jp
New manganese boryl complexes, [Mn(CO)4(PR3)(BH2-PMe3)] (I PR3 = PMe2Ph, PEW were synthesized by the photolyses of MnMe(CO)4(PR3)] in the presence of BH3.PMe3. Complexes uderwent protonation through the action of a Bronted acid with a weakly-coordinating anion, [H(0Et2)21(TFPB) (TFPB [B 3,5-C6H3(CF3)2'41_) to produce the first cationle borane G complexes, [Mn(CO)4(PR3)(q'-BH3'PMC3)](TFPB) 2 Borane complexes 2 were also generated by the methyl abstraction from [MriMe(CO (PR;)] using [H(0Et_2)2](TFPB) followed by the addition of BH3-PMe3.
N"3p Me3P,,,, i TFPB clia gH H' B -HH cc".. I CO hV OC,, I "CC [H(OP2XJ FP8 Mn ' + BH3.PMe3-- . ------Oc" \ ."Cc C)C.,O, % ' N"n, Mn I PR3 -CH4 (DC I 11%PR3 OC I -PR3 co co co 2
HI P2
1 (X-r Y) (DFT)
Compounds 2 are fon-nally the conjugated acids of . However, deprotonation rom 2 did not occur even when they were treated wth bases such as NaH ad dazabicyclOLindecene A Solution of 2 decomposes i a few days to give a mixture containing [MnH(C0 1(PR3)] and [Bl_12-2PMe31+. This sggests the occurence of heterolytic cleavage of te coordinated BH bond in complexes 2 into H- and "[l3H,'PMC3]"'. Thus, the highlyn electrophilic cationic Manganese fragment withdraws electron density of te BH,-PMe3 figand toward te bridging hydrogen atom. 43 CB-7 RU0410027 IIIGIILI'ARN'LAI'EDIC'O. o-'-CB,,",21 AND jc1oso-1-CBqII,.j ANIONS
Colin A. Klner, Mark Thornton-Pett, John D. Kcrinedv and Adreas Franken
Dcpai-iment of Chemisti-y of the University of Leeds, Leeds LS2 WT UK, e-mail: ad)-easf( i cheiiiistiy.lecds.ac.uk
The closo monocarbaboranes [-CB,11-1,11 and [1-CB,,Hg] are the bases of series of weakly coordinatino anions. nteresting for their ability to stabillse highly electrophilic cations and for posse, le practical pplications as catallyst counterions the olefin polymer'sation 12] A iderable 1ocus of current activit-\ d 'ves from the subst'tuent chern'sm, of these cons eri monocarbaborane anions, and how their low basisitles can be tuned by particular substituents for particular purposes. The series of C-arylated monocarbaborane anions are now easily svrithesised in relatively hh yields va the 'Brellochs method', starting rom benzaldehyde
and te common polyhedral borane 17ido-B,,H 4 This presentation deals with aspects of 13- arvlation of te C-arylated monocarbaboranes wich nicely extends te available substituent chemistry, as well as yelding nterestin ad potentially useful new architectures.
1. C.A. Reed. Ace. Chern. Res. 31 1998) 133. 2. S.H. Strauss. Chern. Rev. 93 1993) 927.
44 CA-8 RU0410028
SYNTHESIS OF NEW HYDROXYLATED closo-DODECABORATES Bj2H12-,,(OF1)n 2-
B.Brellochs 1, A.Semloshkin 2
Ludwig-Maximilians-UniversittitMi nchen, Department Cheinie, Butenandtstr 513, Haus D, 813 77 Miinchen, German v, e-mail.- b. brellochsCtbgmx. net
2 A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 11 7813 Moscow, Rssia, e-mail.- semiCaineos.ac. il
Our continuing interest on the substitution of closo-B,,H,, 2-_anions (n=10-12) alms towards facile, reliable and rational introduction of a broad variety of substituents 12]. These functions can be used for BNCT or material science purposes via further linkage to other substrates. We focuse our research on water-soluble functionalized derivatives like hydroxylated 2- dodecaborates B12HI2-,(OH),,?-. B12H12 reacts with various oxidizing aents 'n aueous solution. Despite the mono-hydroxylated B12HI(OH)2- our knownledge abOLIt III-her hydroxylated dodecaborates is only scarce. Depending on the reacent (acetonei'llCl
H2SO4 conc., H20-1) and the reaction conditions we are able to synthesize a krhole series of oligo-hydroxylated dodecaborates 131217112-JOH), 2- (n 1-4 12,3,4 in hgh yields:
OH 2- Oul 2- OH 2- oil 2-
OH OH HO Oil OH H
OH
2 3 4
Durin- te reaction with excess HO a single B,H5(OH)- 2- isomer can be isolated. With this whole range of newly accessible polydentate csters w are able to develop a promising chemistry of oxygen-bridged polyboranes through condensation reactions.
1. I.B.Sivacv, A.A.Serriloshkin, B.Brellochs, S.Sjbbcrg, V.I.BregadzePollhedron, 9(2000), 627 2. A.A.Seniloshkin, P.V.Petrovskii, D.Gabel. B.Brellochs, V.I.Bregadze Rss.Chem. Bull., 1998,47,5950
45 CB-8 RU0410029
BORON-CONTAINING PORPHYRINS A NEW SYNTHETIC APPROACH
a a'b a-b b V.A. 01'shevskaya M.A. Guil'i-nalieva ,A.V. Zaitsev , V.N. Luzgina. b, a r R.P. Evsfigneeva P.V. Petrovski , .H. Morris and L.I. Zakhar:k:ig
A .X A`esnievanoi- Institute Organoclement Compounds, Russian Academy of Sciences, 28 Vavilova str., 19991 Aloscow, Russian Federation. Af I Lotnonosovlfoscow State Acadeniv o Fne Chemical Technology, 86 Vernadsky Pr.,
1 171 Moscow. RUSSiaI7 Federation
Deparimcnt (PUIT a17d,4pj)1ied Chemistrv. Sirathelrde University, Glasgow, GI A7 UK
CurrentlN. considerable attention is paid to the synthesis of carboranvl-substituted heterocycles
for the use as pharmaceuticals for te boron neutron-capture terapy (BNCT) of cancer.
In this communication we report te snthesis of carboranyl porphyrins with enhanced
hydrophilicity based on synthetic and natural porphyrins.
Usinc, svrithetic 2-formyl-5,10,15.'-?O-tetraplienylporpli ,rin and its copper ad cobalt
complexes in the reactions with 1ithium-o ad lthium-m-carboranes ad 1thiurni-nonocarbon
carborane, we prepare etral nd anionic o-, in-carboranyl and anionic monocarbon
carboranyl porphyrins, containing hydroxy roup at the position 2 of porph Tin macrocycle.
Natural carboranyl-containing porphyrins were first synthesized using protohemyn X
(a prostetic group of hemoglobin).C CombiningIn cationic protohemin IX with variou tpe Of boron polyhedra allowed preparation of boronated porphyries of various nature (see below).
H II C C I R=R,= H 11 R, R, N C111 CH-CH, V -0 CII 4IN 3- 3 M=Fe - cl- M=Fe - 0- N, R=R2= C1 1. CH3 + C1120- PhCHO- M=Fe I I P41 L_ I C p - III R1 011:R- IN' R,=01IR2 COR COR2 M=Fe M-Fc
Synthesis of the other natural amione porthyrIns wl be presented and discussed.
46 IA-7 RU0410030
ARACHNO-CARBOR-ANE ANIONS AND THEIR NIETAL COMPLEXES
Zuowel Xle
Departments of Chemistry,, The Chinese University of Hong Kong, Shatin, New Territories,Hong Kong, Chin, e-mail: zxie )'cuhk. edu. hk o-R2C2BoHo R = H alkyl, aryl) can be reduced by alkali metals to give 'carbons-apart' dianionic species [nido-R2C,1310H 10]2- in which the two cage C atoms are in meta positions. Excess alkali metals cannot directly drive,)-carborane to arachno-carborane. However, in the presence of transition metal halides o-carborane can undergo four-electron reduction to form a arachno-R2CAoHlo4- tetraamon with excess alkali metals 12]. It is noted that two cage carbon atoms are further separated in arachno-R-2C21310H104- tetraanion. We have recent1v found that the two cage carbon atoms remain adjacent in ortho positions during two-electron reduction process if they are linked by a short bnidge 3]. It is unprecedentedly discovered that
,u-1,2-[O-C6H4(CH2)21-1,2-C2BOHIO can be directly reduced by lithium metal to give a novel 'carbons-adjacent' arachno-carborane tetraanion 4 This arachno-carborane consists of one open six-membered C13_1 face and one open five-membered C133 face that share one common edge of C-C bond. The synthesis, structure and applications of new arachno-carboraneanions will be presented in this lecture. The effects of the central metal tons, solvents, and alkali metal ions on the molecular structures of the resultinc, metallacarboranes will also be discussed.
1. Xie, Z.; Yan. C., Yang, Q.; Mak. T. C. M. .4ngew. Chem., nt. Ed. 1999, 38, 176 . 2. Chui, K.; Yang, Q.; Mak, T. C. W., Lam, W.-H., Lin, Z.; Xie, Z. J.4m. Chem. Soc. 2000, 122, 5758. 3. Zi, G.; Li, H.-W.: Xe, Z. Chem. Commun. 200 1, I I IO. 4. Z, G.; Li, H.-W.; Xe, Z. Oroanotnetallics2001, 2 336.
47 IB-7 RU0410031 TWO-ELECTRON AROMATICS CONTAINING T I REE AND FOUR ADJACENT BORON ATOMS
C. Prasang, Y. Sahin, P. Amsels, W. Mesbah, G. Geiseler, W. Massa, M. Hofiriann 4and A. Berndt
Fachbereich Cheinie der Philipps-LTniversildtAfarburg, Geimany Anorganisch-ChenzischcsInstiti dr niversital Heidelberg, Gernially, e-mail: bei-ndto,cl7eiiiic.iini-niat-bzirgde
The series of folded four-membered two-electron aromatics comprising long now I 1 and 2 2] was completed by the first derivatives of 3 and 4 Compounds 14 posess eght cy-electrons each to connect the four toms of the rina skeletons.
2 3
0 0 2n electrons 2a electrons
Planar four-i-nembered two-electron aromatics 5 and 6 with only six and four electrons, respectively, in the 7-skeleton of the four-membered rings were prepared, too. The three-membered analogs of 4 and 5, the two-electron aromatics 7 and 8, are known from computations only 3]. Compounds of type 9 which can be regarded as first derivatives of 8, were obtained from compounds of tpe 4 and 6 A dboracyclopropane 10 was generated by methylation of 3 and as shown to contain a planar-tetracoordinate carbon atom, which is the first one without neighboring etal centers. Compound 10 easily rearranges to 11 A closely related migration of a hydrogen bridge was predicted 41 for te prototype of 10 with a hydrogen bdge instead of the boryl bidge.
J
7 8 9 10 1 1 1. M. Bremer. P. von R. Schlever. U. Ficischen.l. m. Cheni.Soc_ 1989,111. 1147. ref. cited therein. M. I fildenbrand I . 16tzko" W ScherLAi7gc-w Chenz. Mt. E D vl. 1985,24.759. ref. cited therein P. 1i. M. likelier. K. Kr02h-.leSPC1_SCn.'F. Clark. P. von R. Shlever..1 Ant. Cheni.Soc. 1985.107,2723. A.A. Korkin. 1'. von R. Schlever. M-Mckee. Inorg. Chem 1995.341 91. ref. cited terein. 4. S. Fau, G. Frcriking, Theochem 1995,338,117, K. Srger. P. vo R Schlever, Theocheni 1995,338,317. 48 CA-9 RU0410032 METAI,-ASSISTED POLYHEDRAL CONTRACTION REACTIONS OF MONO- AND DICARBON CARBORANE SYSTEMS DERY `ED FROiM nido1c1oso-CBjjjnido-C&), nido-CA and evo-nidt)-CAM (),1=0s)
Ir'na V. Pisareva', Vitalli E. Konopleva Elena V. Balagurova', Alcxandr . YarlovskV, Fedor M. Dolgushin', Dmitrii N. Cheredilln', Igor T. Chizhevskv" Andreas Frankenl', John D. KennedY'
'A.N. Nestneyanov Institute of Organoelement Compounds, 28 P`avilov Str., 119991 Moscow. Russia
bScool of Cheniistt3%The University of Leeds, Leeds, LS2 9T, England.
Treatment of metallacarboranes in the presence of a base under thermal conditions is known
to be eployed for their partial polyhedral degradation equently resulting in Structurally novel metallacarboranes. Herein we present a new synthetic approach to middle and sall metallacarborane sstems starting from different mono ad dicarbon carboranes (i.e. nido- CB10, nido-C,138, closo-C1311, and nido-1-PhCB,)) via their polyhedral contraction reactions in the presence of 16-electron complexes MCI,(PPh-)3 (M = Ru. Os) as promoting agents. It is demonstrated that under the reaction conditions used C1,(PPh_-,1), in hot acoholic or aromatic solvents), the elimination of one, two or even four boron-containing fragments from
carboranes is occurred to form eleven-, ten-, eght-C and seven-vertex nietallacarboranes wth mono- and binuclear cluster structure. In some cases. the reactions were ound to roceed with high selectivity of the principal products. The following systems obtained bv this and reiated methods will be discussed with attention to their electronic and structural peculiarities:
H PPh, H 11 R PPh- Ph PPh3 PhY PPh-, PhP PPh,_,f I 3P ,, Os1, \ CT>7-Ru _C1 Ru, Cl_ RLr- PP111 R R R_ ONIe / 0 R R2
R_= Mc R =fl,-O\le M Ru. Os; R (ONIc),, 1-3 N = Os: R.R o-Cl 1Cj LICi 1, 0 = C-Ph R I PPI13- CI Ct 1 C-Ph M = RU: I I R 2 (ONIC)0 1-3, PP113 0 C 0 C1 i, C-Ph
This work was supported by the Rssian Foundation for Basic Research Grant No 00-03- 32824) and, in part, by te UK DTI nd U EPSRC.
49 CB-9 RU0410033
ELEMENTOORGANIC COMPOUNDS WITH NIAIN-GROUP HYPERCOORDINArED CENTERS
Ruslan M. Minyaev and Tatyana N. Gribanova
Institute of Phisical nd Or-anic Cheniisti-i% Rostov State Universiti 19412 Sachka Ave., Rostov-on-Don 344090, Russian Fcderaiion.e-mail:rn1nyaevCq ipoc.rsu.ru
The conditions at hich main-group elements exhibit valent planar and pyramidal hN ercoordinations in elemcritoorganic compounds have been analyzed. The examples of rather stable elernentoomanic compound with planar ad non-planar hy I I - I _percoordination of , C, N. 0. F, Si. PictoLenes. Chalchouenes.Z C1 are -aven bsed on te hll- evel theor--ticalab initio calculations. Special attention is addressed to planar aromatic compounds 14 hypercoordination of boron, carbon and nitro2en centers.
H _BI >\ C B-B B-B B 8 X Y X X I //I\ / ' X:: B B B B B B B B ' 6 B H C B B C H
1, X=NHO; Y=CB- 2 3, X=C-,N 4, X=CSiP- It as been shown that the aromaticity of elementoor-anic compounds increase with increasing hypenalent bonding of hypercoordinated center wt srrounding ligands. Apart frorn planar compounds, hypothetical bi-pyramidal 5 and pyramidal 6 compounds with hypercoordinated main-group centers are presented and teir structural stability is analyzed based on stability of streoelectronic structure. X X jd- BH H B HB-- // BH
Y 5, XY=BH-,CHNO 6, X=O '-,OH- F Russian Foundation for Basic Research (grant 0-03-32546) and INTAS (grant 00-00179) have financially supported this work.
50 IA-8 RU0410034
SYNTHESIS AND PROPERTIES OF LINEAR, BRANCHEDAND CYCLIC METALLACARBORANE OLIGONIERS
Haijun Yao, J. Monte Russell, Mchal Sabat, and Russell N. Grimes
Department of Chemistry, University of Virginia, Charlottesville, VA 22904 U.S.A., e-mail.-rng Cct virginia edit
A rapidly developing area in organometallic chemistry centers on polynuclear metal coordination compounds having specified highly symmetric geometries such as sares, triangles, rectangles, or rigid rods. Interest in such molecules arises in part from their unusual, aesthetically appealing structures, and on the possibilities for assembling them into extended systems having useful electronic, optical, magnetic, catalytic, or other properties. Given their characteristic thermal and oxidative stability, chemical versatility, and relatively low-bulk, metallocene-like steric requirements, small metallacarboranes are attractive candidates as buildings blocks for such structures. Recent work in our laboratory on methods for achieving controlled Sbstitution and linkage of these clusters has opened the wy to some new metallacarborane "desioner" chernistry that will be described in this report.
Z5 Co Ck:\B
B B
Co Co
5 1 IB-8 RU0410035
('111--111STRY OFELECTRON-DEFICIENT METAL ALKYL COMPLEXES OF EARLY TRANSITION METALS: RE;kCTIVITYOF THE CATALYSTACTIVATOR
B(QF. ;b
Manfred Bochrnann
I Vo il 'W;7 11 icriaIs find Catah'sis Cen ti-c. SCII 001 Of C17cmical Sciences, Un h -cl-sill, of East
.4n-lia,I Noi-ivichVR4 7TJ. UK, c-mail in.bochmannoauca.ac.uk
B(C'J_ )-, is a A dek pplied activator for metallocene-based olefin polymerisation catalysts, chosen oi te ha ;Is of its stron- Lewis acldltv and' resistance of its B-C bonds to hydrolysis an I oweer. with suitabl% eectrophilic metal systems, notably half- sandwich compj-_xes. B(C6F )-, can underao a varietv of reaction. ran-Ing from smple C6F5 exchang t prticipation in C-H activation ad formation of ne, N boron-heterocycles.
Examplcs are ricrlons involving complete loss of all tree j substituents to give borole lhjnds, te formation of dizirconlurn tripledecker complexes, and te synthesis. catalytic application and decomposition pathways of new "non-coordinating" BQl` )3-based anions.
Ai-, example of such an anion I'S [lJNjB(C6F5)3j11_, the Structure of xvhich is a raro example
Of' 1L[ItIPIC ... F hydrogenID bondingt=l A protocol for the quantification of boron-based COLIntcranions for cationic catalysts in o1cfin polyi-nerisation reactions as been developed.
The reactivity of roup 4 transition metal compounds will be contrasted with te cemistry of main grOLIJ) CICIIICI]tS, in particular alumimum and zinc alkyl complexes. CA-10 RU0410036 BORANE BASED DIHYDROGEN-BONDED NETWORKS
Caroline O'Dowd, L-uise Brown, Udo D&fler. John D. Kennedv and Mark Thornton-Pett
Department of Chemistry of the University of Leeds, Leeds LS2 VT UK e-mail: marktp(&chem.Ieeds.ac.uk
Uniquely for a first-row pblock element, boron has a lower electronegativity compared to hydrogen. The polarity of a B-H bond is thus the reverse of that of an X-H bond, where X is C, N, 0 or F. Any boron-based compound containing both types of bond can terefore gve rise to the intramolecular and intermolecular hydridic-protonic type of dhydrogen' attractive interaction shown in the diagram below 1]. There is much current interest in this d1hydrogen bonding' (DIIB) not least because, like classical hydrogen bonding (HB), DHB can signifi- cantly affect physical properties 2 It is therefore somewhat surprising that, unlike their classical HB counterparts, not many sgnificant attempts have been made to analyse and delineate DHB networks. The neglect of detailed analyses of DHB networks is unfortunate because many interesting architectures deriving from patterns of ntramolecular and inten-nolecular DHB interactions have gone unrecognised.
B H X = C N, 0 F 6+
Such deficiencies may be explained in part by the lack of a sstematic tool to aid 'the ucid- ation of solid-state architecture and thence help define such networks. We have recently shown that the Kitaigorodskil's Aiijbau Process (KAP) that is based on close-packing principles can be used to delineate solid-state features includin- DHB networks 3 This presentation uses KAP to describe the variety of interesting DHB networks that are observed in a selection of complexes.
1. T.B Rchardson, S. de Gala and R.H. CrabtreeJ Am. Chein. Soc. 1995) 117, 2875. 2. R. Custelcean and J. E. Jackson, Chem. Rev. 2001) 101. 1963 3. C. O'Dowd, S. Sea, J. D. Kennedy, T. M. Polvanskaya, V. V. Volkov, W. Clegg, S. J. Teat and M. Thornton-Pett. 2002) submitted toJ. Chein. Soc., Dalton Trans.
53 CB-10 RU0410037
NEW ASPECTS OF BOROXINE CHEMISTRY
M'chnel A.Beckett,' pen-Hankey, ad K. Sukurnar Varmai'
Chemist)y Dej)artinent, Univei-sitv of[Vales, Banaff, Gwynedd, LL57 2U, UK, e-mail: m.a.becke1tCa,,bangoi-.ac.uk Pilkiii-ton BuildinuroductsR & D, Em-opean Technical Centi-e, Lalhom, Lancashh-e, L40 5 U UK
Pol-vi-neriC 2CIS ae formed bv reactions of metaborate esters, R0)_-B-,0-, with etal alkoxides 'M(OR) M S T. Zr). Tese els. formed bv a series of condensation and elimination reactions. may be di-led (60`0 and then fired at 600T to 'yield MO,. For M Si a consi rable quantity of remains within the O, etwork and an amorphous alkali-free borosilicate -lass is formed 1]. With M = T ad Zr, crystalline phases of anatase (TiQ) and tctrauona1-Zr0- are obtained. Metaboratc esters also form els or polymers upon reaction with isocyanates or dilsocyanates 2 e believe that these products retain the boroxine ring molet ad arise frorn alkoxvboration of the CI bond of te isoevanate. hese aterials are
1iNdro1vtIca1]V Unstable and are readily hydrolysed to carbarnate esters and B(Ofl .
Orthoborate esters are generally unreactive in the above systcins. Tills -difference in
rcactikity may be rationalized in terills of the relative clectroplillicities of the centres 'In the
orthoborate ad riletaborate esters. Te Lewis acidity of a series of halogenated akyl
metaborat ad orthoborate esters have been estimated by Gutmann's Acceptor Number (AN)
method ad tese show an expected correlation with Taft's 7* sbstituent constants 3]. The
pci-fluroarylboroxine (C(,F50303 (AN - 5) displays acidic properties typical of a metaborate
ester nd its potential as a catalyst in or,,anicZ: transformations is to be investigated.
I MA Bckett'. M.P. Rugen-Hankey ad K.S. Varma, Chem. Conzinun., 2000, 1499.
M.A. Beckett, M.P. RLI-en-Hankey, and K.S. Van-na, Main Gi-oup Metal Chem, 2002, 25,
(8), 485.
3 MA. Beckett, M.P. Rugen-Hankey, and K.S. Varma, Phosphoi-its, Siffur und Silicon, 2001,
168, 437.
54 IA-9 RU0410038
"BORON CLUSTERS, DO THEY RECEIVE THE DESERVED INTEREST"" Francesc Telxldor Institut de Ci ncia di.Waterials de Barcelona (CS10. Canipits L .4.B- E-0819J Bellaterra, Spain, e-mail.- teixidor(c-v --mab.es Boron clusters, boranes, carboranes, display many particular characteristics that do not find parallel in their organic counterparts. On the other hand the chemistry of carboranes seems to be very much related to organic chemistry. This is why in attempting new reactions chemists working with boron clusters check organic chemistry reactions as a source of inspiration. The opposite is, however, seldom true. The view of boranes or carboranes as rre, strange or esoteric, in addition to have high price and an assurned, unrealistically, low staillity precludes synthetic scientists in other areas to overcome thinking on these Csters as real building blocks. The advent of materials science with emphasis in new tridimensional structures should correct this vision. One way to look at the more versatile borane, the carborane, is as a free rotatin- benzene ring. Te occupied volume is practically the same but the o-carborane contains twice as many atoms and beams are exiting radially in any direction. For stance -
C615 Culd be compared with -QB 1011 1. Both have the same rotating volume, but the cluster 'des twice as many possibilities n any drection of space. This s a very little exploited characteristic that can becorne very relevant. Both benzene and carborane are considered to be aromatic. In benzene rn-s modulation of the C-C distance is not easily done and the shift from typical bonds is minor. In o-carborane this is relatively easily done. Concerning the electron-witildrawing caracteristics of o-carborane, to the moment the shortest I ... I distance in spoke like RR'R"P-1, charge-transfer complexes has been achieved when R" is an - carboranyl fragment, also showing the uqueness of these clusters. More on it. 'he only example of I- entrapping with phosphine compounds has also been produced when one of the P substituents was o-carboranvl, and the arrav P... I... I... P was obtained. This provides the opportunity to generate suprarnolecular structures besides the ore conventional hydrogen bonds, 7i n stacking forces, electrostatic interactions, among others. Again it seems that the isotropic dstribution of beams in anionic clusters may account for the highest over oxidation stability of conducting polymers reported to now. As a final example the Custers provide the opportunity to rnimic or to widen the possibilities enerated by organic lgands. In tis sense the cyclopentadienyl ligand Cp is perhaps the most popular ligand in or-anornetallic chemistry. Its dicarbollide nalog [CB,)HI 112- coordinates in a similar wy bt stabilizes higher oxidation states, but it can be the basis for Cp like complexes with dfferent geometric posse I es.
5 5 IB-9 RU0410039 UTILITY OF BORON CLUSTERS FOR DRUG DESIGN: SELECTIVE ETROGEN RECEPTOR MODULATOR (SERNI) BEARING CARBORANE AS A HYDROPHOBIC SKELETAL STRUCTURE
Yasuvuk Edo,' Tonnobiro Yoshimi' and Chisato Myaura b
Tohokii PharinaceuticalUniversitv 44-1, KoniatSUS17inia, Aoba-kzi, Sendai 981-8558, Japan
e-niail:.vendooatohoku-pharm. acjp
SChO01 0fP17a1-1?1a(T, Tokyo University Pharniacrand Life Sciel7ce. 1432-1, Horinouchi,
Hachioji, Tokyo 9-1-0392, Japan
The olecular sape and hydrophobicity of dcarba-closo-dodecaboranes may allow a
neA niedicall appilcation as bologically active molecules that interact hydrophobically with hornione receptors. Recently., we have reported te design snthesis and bological activities -)f cai I Ing estrogen receptor ag Ing c -borane-conta'n' - -onists. Te most potent cornpOUnd bear' carborane ca-c (BE120, 1) xhibited activity at least several times zreater than tat of 17fqC tj-,ld 01 'II ILIC'fei-asereporter,-,eneassayandestrooenreceptora(ERu)blndintidata [1].
We also designed and snthesized estrogen antagonists on te basis of the structure of
BE12 ad that of tpical estrogen antagonist, tarnoxifen. Amon 9 them, we noticed the characteristic features of compound (BE360 2 having carborane cage and two phenols. The
ER bindinc, affinities of BE360 are 1.6-fold to ERa and 0.15-fold to ERP compared wth
estradiol. To examine i vivo estrogenic activity of these compounds in bone, ovariectonnized
(OVX) inice wre given BE360 or estradiol subcutaneously for 4 weeks. Treatment with BE360 at 130 mg/day dose-dependently restored bone loss in OVX inice to sham level wthout
estro.ienIc action in uterus.
These results 'Indicate that BE360 binds to ERs and exhibits estrogenic action in bone to
prevent bone loss without inducing estrogenic action in the uterus, suggesting its possible
application to osteoporosis as a new type of selective estrogen receptor modulator.
HO CH20H
HO HO 2 BE360 1 BE120
1. ndo Y iirna, T.: Yamakoshi, Y.. Yamaguchi, M Fukasawa, H.; Shudo, K.J. Med.
Chcni_ 1999, 42, 1501-1504; Endo, Y 11jima, T.; Yamakoshi. Y., Fukasawa, H.;
M 1vaura. C., nada. M.; Kubo, A., tal, A. Chenfistn, and Biology-, 2001, 8, 341-355.
56 CA-1 I
RU0410040 CHIRAL SEPARATIONS OF CHARGED CLUSTER BORANES
Viktor Slavi&k a, Radim Vespalec h
aDepartment ofAnalytical Chemistry, Faculty of Sciences, Palacky University Olomouc,
Czech Republic, e-mail.-slavicek(aiach.cz
bInstitute ofAnalytical Chemistry, Czech Academv of Sciences, Veveoi 97 6 42
Brno, Czech Republic, e-mail: yespalec (Li,iach.cz
Further research on the practical utilisation of chiral cluster boranes, for example for stereoselective homogeneous catalysis, requires the using of their sterically pure forms.
Therefore the existence of methods for their separations as well as the mzthods for the checking of the purity of prepared substances are necessary for this Purpose. Liquid chromatography was successful in chiral separations of uncharged derivatives, hovewer te charged derivatives that are more attractive for the analysis of new compounds are not separable by the technique.
Our contribution demonstrates that capillary zone electrophorcsis is efective instrumental technique for the chiral separations of charged cluster boranes. Racemic mixtures of derivatives of nido-[R-7,8-CB9Hjj]- skeleton, of sandwich complexes of the closo-[R<(1,7-C-ByHl(),-'-17-Co] tpe and chiral binary borane [i-B.1sH-,j]- were chirally resolved using B-cyclodextrin as the chiral selector. The behaviour of the selected species during the separation was studied. too. It was observed that the addition of a polar organic solvent (like methanol or acetonitrile) was necessarv for the reachinc, of the chiral discrimination. Acetonitrile proved to be more appropriate additive than methanol. Its influence on the course and on te result of investigated seprations was studied in more details.
57 CB4 RU0410041
THE 1,1-ORGANOBORATION OF OLEFINIC DERIVATIVES OF TIN
Oleg L. Tok Brnd Wrackmeyer
Laboi-(it,)i-iiiiiiffit-,-Iiioi-a(7i7isc-he Cheinie der Universl'tiit Bayreuth, D-95440, Germuny, C-111ail: oleg.tokCa .iiiii-baii-eiith.dc,, b.iii-ackCauiii-bayi-eitth.de
TrIorganoboranes are well known to react wth acetylenic derivatives of goup 14' elements
to (Tj\,e cv-boroii-eleiiient-substituted olefines [1] Wen te metal atone bears more than one
triple bond the real-ijon leads o the formation f heterocyclic products. Here e report on the
first attempt of using an olefinic derivatives of tin as a substrate in .1-orpanoboration.
The reaction o trjorLanoborane with dmethvIdivinvItin at roorn temperature gives
almost qUantatively a trans-disubstituted heterocycle A. On hting A eliminates
djorLanoborane 1--deliNdroboration) to give either stannalene B R = All) as the only
product or, a mixture of eterocycles A-D with composition depending on tile nature of the
triorganoborane
R R (Scherne 1). Me2Sn + R3B - Me2Srlo A Me2Sn -112 (BHR2)2 Dimethylbis(propen-2- A BR2 B YI)tm reacts with
R= Et, All. H=CH2, 1/2 (BHR2)2 trior(yanoboranes much -CH2PhPh, z:1 cyclo-Pent R 112 (BHR2)2 Me2SnC R slower compared to Me2Srj dirriethy1divinyltin. C R2B D However, the action
Scheme I proceeds faster with
d1organoboranes (Scheme 2 The triorganoboryl moiety forilled after 1,2-hydroboration
reacts further wth the remaining double bond by 1 I -or(yanoboration mechanism to give a Me Me R11, heterocycle of the type E. It's important to note R'2Sn + R2BH Sn 3,BR2 >== R" that one of the methyl groups in the product E Me E R213H = Et2BH. -BBN occupies the vicinal position relative to tin R'= Me, Ph Scheme 2 atorn. This fact strongly supports the ],I-
onianoborallon mcchanism accompanied wth carbon-metal bnd cleavage.
1. B. Wrackniever, Cooj-d. Chem. Rev., 1995, 145, 125.
58 [A -10 1111I 1[ 11 1111 1111 1[ 111 1 I RU0410042
REACTIONS OF BORANES AND METALLABORANES WITH PHOSPHINES
Lawrence Barton. Oeo- Volkov, Mtsuhiro 1-lata, Paul McQuade Ngam P. Rath
Departnient oj'Chemistn' Univ of'Missoia-i-Sl. Louis, St. Louis MO 63121, USA, e-maik lbarton(w umsl.edu
This presentation will cover several aspects of recent work, all of which involves the formation of phosphorus to boron bonds. Recent results involving the formation of linked clusters based on reaction of rigid backboned bidentate phosphines with I(PPh3)2(CO)OsB5Fl')], and subsequent derivatization of the products will be described. An example of the species formed is [212,2-(PPh3)2(CO)-iii io-2-OsB-IH7-3- BH2-PPh21Fe(C5H4)2j-PPh,-BH3j. Reaction of bidentate bases with the unsaturated clusters [8,8-(PPh3)2-nido-8,7-RhSB9Hjo] and [9,9-(PPh3)2-tiido-9,7,8-RhCBgHll] will also be described. We have extended our previous work and performed a range of organometallic chemistry on both of these metallaheteroborane clusters leading to the isolation of such species as [1-(PPh3)11,3-( t-dppm)'-closo-1,2-RhSB9H8], with a dpprn Molecule brldv- I a metal to boron linkage, [1,1-(q 2-dppe)-3-(Tll-dppm)-clo.yo-1,2-RhSB,)H, ], involvincy mixed ligand systems, and [9,9-Tl'-J(fl"-BH3)PPh2PCH2PPh,',-iiido-9,7,8-RhCBSHII] which contains a bidentate dppm-BI13 molety. Linked Csters based on bidentate phosphines, such as [BH3.PPh2(CH),,PPh?.IrCp*Cl,] will also be described. An example of a phosphine- polyhedral borane which we will describe is [NR4][BjjHj,-(dppm)] in which the borane cage is isoe'.ectronic wth [BIIH141-. Finally a novel oxidative coupling reaction promoted bv CP2ZrCI2/'n-BuLi to form the new nonaborane ca2e vstern. araCj'7no-B,,H;j-(PPh-), an unusual homoloaue of the well-known species B iH I (PPh-)2, will be described.
59 [B-10 RU0410043
CARBORANE-GADOLINIUNI BINARY SYSTEM AS A NIR UNIAGING BORON
CARRIER
Yoshinori Yamamoto
Departinew of Chel7listi-i-. Grachiate School of Scicnce, Tohoku Univer. io,' Scndai 980-8578
Japan, c-niail.-.ioshi(a-".i-aniai7iotol.chei;i.tohoku.acjp
Th ealuation of the Gd-carborane complex 2 as an MR niaging and boron carrier agent was
carried Out i17 vii o. Te MR i-naging revealed that te carborane Gd-DTPA 2 \vas metabolized
slm\-cr in the body tan Gd-DTPA 1. The results of te ICP-AES ethod indicated that
compound 2 was ncorporated into normal tissues ad metabolized quickly, %%'hereasit was not
accumulated into turnor or brain tssue. The -autoradio-raphy showed tat a high level of
boron was obtained in the internal organs and in the necrosis of tumor tissue.
2- N 2- H 0 02 N------Gd ---- N------Gd ----- N
2 C02 02 2
&02 'C 602 'CO2
Gd-DTPA I Carborane Gd-DTPA 2 CBH
The synthesis of BPA-Gd complex 3 will be also presented.
2-
N - d C' 2 N 2H+ H rb -Q2 j - N C02 C02 H02C B(OH)2
60 CA-12 RU0410044 DIRECT INSERTION INTO CLOSO-METALLAC.kRBOR-ANES
Alexander R. Kudinov*, Dmitry S. Perekalini, Stanislav S. Rynin, Konstantin A. Lyssenko. Gennadii V. Grintselcv-Knvazev, Pavel V. Petrovskil
Nesmeyanov Institute of'Organoetement Compounds Rssian Academy of'Sciences, 119991 Moscow, Russia, e-mail: arkudinovq)ineos.ac.ru
Examples of direct insertion into closo-metallacarboranes are still very rare. We found that the fragments [(ring)M]+ insert into 12-vertex metallacarboranes to give polyhedral expansion products (see examples on the scheme).
Ru Ru N.-
Ru Ru
OT
Co
N i
RU 77 -
Ru
0 0 B The resultin- 13-vertex dimetallacarborancs are extraordinary stable althOLIgh they do not
LI z:1 obey Wade's rules. Te stnictures of the compounds were determined by X-ray diffraction.
61 CB-12 RU0410045
INVESTIGATION OF ELECTRONIC INTERACTIONS IN DERIVATIVES OF CLOSO-BORANES
,,a" a a V Piotr Kaszynsk- Serhii Pakhomov , Krystyria K Kullki ewicz, Michael B. Sponsler,
Minchul Chung, hJoseph E. Williams, b Victor G. Young Jr.c
aOrganic Aate7lals Research Group, Departinent of Chenzistn', Kanderbilt University, A'ashville, TN 37235 USA. Department of Cheinisoy, SVracuse University, Si racuse NY 13244 USA. cA'-rav Cgstalloal-aphicLaboratory, Departnicilt of CheniistrvUniversh of Minnesota, Tivin Cities, MAT55455
In continuation of our interest in electronic effects in 12-, 10- and 6-vertex closo-borane derivatives [11. ve conducted experimenta ad computational studies on tree tpes of compounds: containing triple bonded groups (1). azo groups 2), and phenyl substituents 3) Z Z7 directly connected to the clusters. Results for te cluster derivatives ere compared to those obtained for benzene, acetylene, cubane, and b ,clo[2.2.21octaneI analogs.
Y=X-A-X=Y Ar-N=N-A-N=N-Ar Ar-A-Ar 1 2 3
• Results of experimental (X-ray, spectroscopy, chemical stability) and computational (hybridization and 7-7i overlap) nvestigations of five series closo-boranes and hydrocarbons substituted with triple-bonded groups (C*CH, CN, CO, and NN) are in as4reernent tat the degree of electronic interactions between the cluster and the XY substituent is lowest for the 12-vertex closo-borane and highest for the 6-vertex analog. • Transmission of electronic effects through the clusters has been studied spectroscopically and electrochemically for iron complexes of dinitrilles I (X=C, Y=NOFe*). We have isolated an unusual side product which was dentified as a product of insertion of MeOH into the I 0-vertex carborane cage. • CornpUtational studies of then-nal stability for B0118(N2)2 show the unique role of the apical positions in stabilizing the N2 group. • Spectroscopic studies of a series of liquid crystalline carborane derivatives 2 and 3 supported b ZfNDO//ab nitio calculations show stronger electronic interactions with te I 0-vertex cluster than with the 12-vertex analog. All data indicated that the stron2est electronic interactions are observed for the 6-vertex, which is followed b I 0-vertex ad the wakest for the I 2-vertex borane.
1. Kaszynski, P. n 4nisolropic Organic materials. Aproaches to Polar Order.; R. Glaser and P. Kaszynski, Eds., ACS: WashIngom. D.C., 2001: Vol. 798; pp 68-82. Kaszynski, P.; Pakhomov, S.- Young, V. G. Jr. Coll. Czech. Chem. onitnun. submitted. 62 CA-13 RU0410046
SYNTHESIS AND REACTIVITY OF NEW ALOGENATED BORANES AND CARBORANES
Gemma Barberd,' Francesc Te1x1dor,' Clara VifiaS'a eijo Sillanpdd, Raikko Kvekds'
'Institut de Cncia de Materials de Barcelona (CSIC). Campus UA.B. E08193 Bellaterra, Spain, e-mail: barbera( zjcniab.es, teiyidor(aicmah.es,claraCaicniab.es bDepartment of Chernistty, University of. yvdskyld, FIN-40351 vvdsky1d, Finland, e-mail: resillan Jyuf1 'Department of Chemistry, PBox 55, IN-00014 University ollelsinki, Finland, e-mail: raikkok(a-,,saunalaht1.fi
In the last decade great interest in introducing a large number of substituents on boron in icosaliedral borates, and heteroboranes as been experienced 1. Substitutions have been achieved wth good success with the cluster anions, but there are few examples on the dicarbaboranes. Methods to introduce substituents on the largely studied o-carborane need to be investigated. As it is generally accepted the cosahedral carboranes are aromatic and undercyo Electrophilic Sbstitution reactions, making this method attractive for introducing the cage molecules. Wile perfluorination 2] and perchlorination 3] of dicarbaboranes have been obtained, perbrornination and perlodination has not been accomplished. Before 996 the maximum nmber of lodines in o-carborane as 2 which ere occupying the 912 positions 4]. Little nformation exists on hher substitution, althou-h reference has been ade on odo o- carboranes in 912,8.10 [5] A major progress was recently achieved upon te synthesis of the eight iodine 4,'-;,7.8.9,10.11.12-octa-B-lodo-l.'-I-dicarba-closo-dodecaborane 6]. Therefore the carbons adjacent B(3,6) are resistant to electrophilic methods. It is our hTothesls that o et such substitution-more than one tpe of reactions is necessary. One electrophilic reaction for the electron-rich boron atoms and one nucleophilic for the electron-poor B('),6). Following this strategy we have incorporated 9 and IO iodine atoms into the o-carborane cluster.
W. Jiang, C. B. Knobler M D. Mortinier, M. F. Havvillorne.Angew. Chetn.lnt. Ed. Engl. 995. 34. 1332; B. Gr6ner, Z. Janousek. B. T. Km, J. N. kVoodford. C. 11. V. Vsetk:cka. J. Mchl,.J Am. Chem. oc_ 999, 121 3 2 T. Pevni.,mn. C. 11. Knohler, M. F. lla\\thorne. Chem. Coinmun., 99. 2039; A. Herzo-, A. Maderna. J. N. Harakas. C. B. nobler. 14. F. I avoliorne. Chem. ur. .. , 1999 5, 1212; C. -\\'. Tsang. Z. e, 7hein. Commun.. '000, 1839. 2 S. Kongpricha, 1. Schroeder, Mot-g. ( hein.. 969, S. 2449. 3 H. Schroedcr. T. L He, ina J R. Reiner. Inorg. Cicin.. 1963 6 1092. J. F. Sieckhaus, N. S. SCInClulk, T. A. Kno-vvies ad I . SchroeLier. nor-. Chem I 69. 8, 2452.
4 L. 1. Zakharkin, V. N. Kilin i 11 , 1:7 1. -!Aod..VcmkSSSR, Scr. khim.. 1966 3 575. 5 L. 1. Zakharkin, V. N. Kalinin. Ser.Khitn.. )(69 3 607. 6 R. R. Srivastava. 1). K. I lainfin, 1). S. WilbUr..J. Ori . Chein., 1996. 61, 9041. 63 CB-13 RU0410047 SYNTHESIS AND COORDINATION PROPERTIES OF CARBABORANYLPHOSPHINES
1. Maulana,' A. Sterzlkl P. Unneckel S. Blaurock,' E. R YS2 and E. Hey-HawkinS2
Institut flir Anoruanische Cheniie der Universitdi Leipzig" Germany, e-niaik leli,,ai-z.ziiii-leip--ig.de. -. 4. V Nesnicvanov Institute of Oi-aanoelement Compounds, Russian A cadeniv of Sciences, Moscow, Russia
Or-anic or organo-elerrient drivatives of dcarba- ,-,Ioso-dodecaborafles(12) he received increasing attention durino the ast decade as thev xhibit nteresting chemical and physical pronertics. Thus. tese cornnounds have beer, ernoloved among other applications in neutron-capture therapy of iumors (boron neutron capture thcrapy) [II Died other medical areas. Hence applications in medicine can x be envisioned for related carbaboranylphosphines and transition metal P",R corriplc\es tereof 21. Whiie tertiary phosphino derivatives of dcarba- clo.so-dodecaboranes(12), Miich ere first reported in 1963, have been X = C1 H employed as ligands in ransition metal chenilstrv, and as starting aterials R = Aryl, Alkyl for the preparation of other closo-Carbaboraiie(]'-')-contal'n'lng R'= R H PRX or(-anophosphorus compounds, their secondary analogues and cliloi-olilic)spli,-in ,]-substituted derivatives have remalined largely uexplored, W hve otained a diastercorneFIC mixture of' I,2-(PBu'CI)2CBjj1j( (1) frorn I,2-L12CB10"10 and RPC1,. Pure i-ac ad ineso-1 can be obtained b chromatography. The mono-phosphino substituted drivatives -PBu'CI-2-R-CBjj1jo (R = H. Ph) are obtained silarly. The secondary phosphine I-PBu1H-2-Ph-CBjoHjo 2) is obtained by reaction of te corresponding chlorophosphine \vIth LiAll-14.
(7 --- Ne 7ki C1 P,
rac-1 meso-1 2
Several transition metal complexes were obtained with these functionalised carbaboranylphosphines: rac- and ize, 'o-[MO(CO)4)il,2-(PBu'CI)2CB,oH,c)k], (RRRR1SSSS)- [Cu,(p-CI),! I,2-(PBu'C1)2C2Bji -H10, .21, [AuCl 'II-PBu'CI-C2BioHij ] etc. All carbaboranylphosphines and omplexes, thereof were characterised spectroscopically ('H, 'P, ''B, t NMR, IR, MS) ad in some ca,,es also by X-ray crystallography.
1. M. F. Hawthomc_4igc"-. Chein. 993. 105, 997.
2 At'llu Clliplexes ll Cancel- Cheniotherapjl ed. B. K. Keppler, VCH, Weinheirn, New York,
1993.
64 IA-11
RU0410048 OPENING OF THE CLOSO-NBI, CLUSTERS BY BASES: iNTECHANISM
Peter Paetzo!d, Jens Maller, Franc Meyer, Petra Lomme
Institutfiir Anorganische Chemie, Technische Hochsehule Aachen, D-52056 Aachen, Germany
Neutral bases L or anionic bases V are added to aza-closo-dodecaboranes (I R = H, Me, P1) under opening of two BN bonds, leaving&:I the non-planar pentagonal aperture N1-135-138-139-- B4, and formation of a hydrogen-bridge between the two atoms of connectivity 4.
+or L NR +X- 0 BH. BL or Bx
,,Ak, JL-H
2 3 4 L, X in L position nido-RNB,,H,,L 2 8 c1oso-RNB,,H,, or 3 4 _--!-X - nido-[RNB,,H,,X]- 4 2
Depending on te base and the reaction time and temperature, products of the tpe 2 3 or 4 could be identified. The L_eneral trend is a reaction to give 4 via 2 and 3 by the followingt mechanism (the ineta-belt and the para-B atom are left off for clarity).
L or
66 cl 0 EL, EK ,II, j,- H IF endo H 3 4 i
This mechanism is supported b the openiric,0 process of several, aza-closo-dodecaboranes in which boron-bOLind 11 atoms had bee sbstituted by other roups. On working in deutero- methanol, te extra-H atom is not replaced by deuterium.
65 IB-11 RU0410049
THE ANCHROMOPHORIC SYSTEM
K. Albrecht', M. KZistcr', Chr. Burmester', P. Xavieri', Y. Apeloig b, D. E. Kaufnianna
Instilittflir Organische Cheinie der Technischen Universitt'it,Lcibin'-str 6 38678 Claus- ihal-Zellcifield, Gerinan.1%- e-inaik detei-.kaiiii;iaiiiiC&Iil-claitsthal.de Dej arfnient of Cheinistr-v, Technion Israel Institute ?I'Technolog v, fla fa 32000, Israel
Polarized 7r-clectron sN 7stenis are iportant because they act as chrornophors in organic dyes and. furthermore. are of interest as materials xvith non-finear optical properties used in ontoclectronic techniques. Usually. both electron donating and electron \thdrawing groups are connected 0a aromatic or conjugated olefini 1SN'stems. resulting in a internal charge- transfer band in the UN,-VfS area. Based on calculations of their spectroscopic properties -Nre have synthesized three types o or-anic cives N\ ith different B.A 7chrornophoric svstems. in he trequerifl\ used triarvinethane aves. conjugation is ransferred o\er the central carbeniuni ion. Fonnally Sch a carbenium ion is isoeJectronic wth a s-hybridised boron atom and replacement of the forrneT by the latter leads to the novel class of organic dyes . We have deN ciopcd a general approach to tese triarylboranes. beginning Nvith cornmercially a\a ble startinu mater'als. Te stability could be bv the of two stcricall\ demanding inesityl groups at te boron atom.
N
B N B_ Cr
2
N ' 0 O-B O:E
-N H N-,/\
3 4
With the exception of boroles, only little is known about anti-arornatic boron heterocycles Terefore, we becarne interested in the synthesis and properties of derivatives of the nti-arornatic Sn electron, bicyclic pentalene and ab initio calculations for the parent compound. Combination of nitrogen ad boron within the benzopentalene skeleton led to the first 8-borafluorazene derivative 2. Indigo is the best kown example of a cross-con'tigated chrornophoric system. Substitution of' te carbonyl groups by boron lds to the first example of the parent cis- chrornophor 3 A potential tpe oil' precursor olecule to a d1boraindigo dye is represented by th.- benzoazaborol 4. Especiall\. the BA des of typ I sow a strong fluorescence with very high quantum yields and strong solvalochrornic. effects.
66 CA-14 RU0410050
FIRST DARSADICARBABORANES ANALOGUES OF THE ELEVEN-VERTEX TETRACARBABORANE C4B-1111 SERIES
Libor Mkuld, ek', Bohumir Gr ner', B. tibr' and lvana Cisafovd
Institute of Inorganic Chemistry, AcademY of Sciences of the Czech Republic 20 68 fief near Prague, Czech Republic, e-inail: mikulasekCtLiic.cas. cz,
b Department of Chemistry, Facuh v of Natural Sciences of the Charles University, Hlavola 2030, Prague 2 Czech Republic, e-mail: cisarova(anau1ur.cuni.c_-
The reaction between the arachno dicarbaborane 4,6-C2B7H]3 and ASC13 or As, in dichloromethane in presence of Proton Sponge 'R (PS; 1,8-dimethylaminonaphtalene) resulted in the isolation of two novel parent nido-diarsadicarbaboranes 7,8.9,Il-AS2C2B7Hq 1), 7,9,8,l0-AS2C2B7Hq(2)(inyields: and%)and3-CI-7,8,9,11-AS2CB71-19(3)(or3-1-7,8,9,11- AS2C2B7H9 4 respective halogenoderivatives. The reaction between the isomeric dicarbaborane arachno-4,5-CB-H13 and AsC13 in dchloromethane in the presence of PS provided a different asymmetric isomer nido-7.8,9 I O-AsCB7H9 (5) and its chloroderivatn,'e 3-Cl-7,8,9,l0-AS2C2B7H,) 6). Analogously to the ormer series, the isomeric nido-7,9,8.10- AS2C2B7H9 2 was solated as the minority product. The structures of compounds 4 and 6 were determined by X-ray diffraction analysis. In addition, the structures of the solated compound were geometry-optimised and confirmed by comparison of experimental and calculated "B chemical shifts and peaks in infrared spectra. The calculations were perfon-ned also for the missing member of tis family. the nido-7,l0,8,9-AsCB7H,, isomer. which has not been fnd between isolable products. The new compounds are structural and isoelectronic analogies of the already known species from the PC-B-H- diphosphadicarbaborance 121 and C-113-H I tetracarbaborane [3. 4 series. The partial support from the The Ministry of Education of the Czech Republic (Pr 'eel LN 0OA028) and the Grant Agency of the Czech Republic (Grant No. 203/00/1042) and is appreciated.
1. tibr B. et al., Chem. Eur. J. 2001 7 1546-1554. 2. Holub, J., Ormsby, J., D., Kennedy, R., Greatrex, R., kbr, B. norg. chem. Commun. 2000, 3, 178-181, 3. Jelinek, T., Pekk, J., Mareg, F., flcftn nck, S., fibr, B. Polvhedron. 1987 61737. 4. tibr, B., Jelinck, T., Drddkovd, E., 11'efmdnek, S., Pl6ek, J. Polvhc lron. 1988 7 669-680.
67 CB-14 III I 1[ 1 II I I1[ 11 III I 11 RU0410051
ALLYLBORATION OF NITROSO COMPOUNDS
D. G. Pershin', M. E. Gurskii3, T. V Potapova', A. L. KarlonovaYu.a N. Bubnov' b
"A'. D. Zelinsk-17 Institute of Organic Chcniisirv, Russian AcademY of Sciences, 11 9991. GSP-1, Leninskyprosp., 47, Moscow Rssia. E-mail borCqcacr.ioc.ac.ru -anov Institute of Organoclement Comj)ounds, RussianAcadcm of Sciences, 4A. Nesmci I!> 119991. Vavilova str., 24, Moscow, Russia.
Nitroso'henzene reacts with tr'allvl- and tricrotvIboranes at 70 N orn-iing two 12- addition roducts I and 3 in a 3:2 ratio in each cares (NMR). the deboration of which lead to
the corresponding 0- 2) and Aallylated pheny1hydroxylarrilnes 4).
R R R
01' I TEA O N I I - "I Ph N Ph 13 Ph B 2a (R- I ), )3 PhN=O TEA la, lb 2b R-Mc) 100-1 10 R
-70'C TEA PhNH R ' )B Ph R Ph R Ph 5 N N TEA
]FA NCI'2Cf"0")- O B B OH 4a R=H), 3a, 3b 4b (R=Me)
The reductive allylboration of the nitroso-group proceeds completely with allylic rearanclement via te six-membered transition state similarly to all other allylboration reactions). The compounds I a and 3a react with triallylborane 100-1 I 'C) to frrush, after
deboration wth triethanolamine, N-allylanilines 5. Allylboration of I nitrosoadamantane proceeds at 20'C and leads to compounds 6 and 7.
N=O ' " O" N-BAJ12 N-0BAI12
~)3B
THF, 20'C +
6 6:7= 1:1 7 This ork was supported by RFBR (Grants 0 1 03-32465, 00-15-97378 and 02-03-32248).
68 i I CA45 RU0410052 SYNTHESIS OF FUNCTIONAL DERIVATIVES OF THE 12-C134-11jil ANION' Igor Sivaev, Stefan Soberg, Vladimir Bregadze j - -
A. N. Nestneyanov Institute of Organoelement Compounds, Russian.4cademy o Sciences Vavilov Str. 28, 119991, Moscow, Russia, e-inail: sivaev Cvimeos.ac.rzi, bre(iJneos.ac.1-u Department of Organic Chemistry, Institute of Chemistry, Uppsala Universin, P.O. Box 531, S-75121, Uppsala, Siveden e-mail: SSJCciketni.uu.se
Recently we have developed several new approaches for synthesis of functional drivatives of different types of polyhedral boron hydrides, such as closo-decaborate anion [BI(HI012-, closo- dodecaborate anion [B12H12 ]2-, cobalt bs(.dicabollide) anion [3-Co(l,2-C2B9Hj1)2j-, for nclear medicine. In this contribution we report synthesis of functional derivatives of the 2-carba-closo-decaborate anion [2-CB9Hj0]- anion based on a simple two-stage method proposed by Brellochs [1]. The reaction of decaborane(14) in alkaline solution with various aldehydes RQ0)H (R = H, QH . 4- C6H4Br, 4-C6H4NHCOMe, 2-C6H_4OMe) results in arachno-[6-R-6-CBJHj.]-and nido-[6-R-6- CB9Hjj- carboranes. Oxidation of both arachno- and nido-derivatives with iodine in alkaline aqueous methanolic solution gives the corresponding c1oso-[2-R-2-CB,)H9]- carboranes.
H R IH
7- H H arachno-16-R-6-CR IF13 R-- H R El,2-C61 'IONIC
OF], 0 W H R7 BjoH14 12-R-CB,"'T
llz nido-16-11-6-C K, H II R = C6115, 4-C6 1, Br, 4-C611IN11CONIe Halogenation of the closo-[2-R-2-CB9119]_ carboranes and sonic other their transformations wre studied. This work was spported by INTAS 99-00806), te Rsian Foundation for Basic Research 02-03-32192), the Swedish Cancer Society ad the Carl Try-gers Foundation.
1. B.Brelloclis I: Contemporaty Boron Chemistrv, K.Wade, M.G.Davidson, AX.11tighes ad T.B.Marder, Eds., Royal Chemical Society, Carnbridoe, 2000, P.212.
69 C B15 111 I I 1 111 I[ I[I 111 11 1 III RU0410053
SYNTHESIS OF THE NOVEL CARBORANES BASED ON -13120MOMETHYL-0- CARBORANE
A. A. Sernioslikin, M. V. Vichuzliamn, V. 1. Bregadze
A. A'. Aesinevanov Institute Of 01-ganoelemenI Compoinuls, Russian Acadeniv q Sciences, 28 1al-ilova str., 119991 Moscow, Russian eM-alion, e-inaiksemirq ineos.ac.ru
I -Brorrionnethyl-o-carborane 1) is ratio easily prepared organic carboranes. There are tree possible ways of its modification:
H /-.\u NU H -Br g H\\ AlpBr E_ H E 'W ------0 0 BI(HIo BI0HIo BioHlo BloHlo (way 2 1 (way MR
M Br E - Br E \0 ------\\0711 BIoHjo BI(Hjo (way 3) Synthesis of 1-bi-oiiiometlivl-2-lithio-o-carborane, its reactions with electrophiles and further transforniations of some novel adducts wll be discussed.
RI 0 Rr- RIR)CO Li PX R Q Br Br Blollio Blolijo BIoHIo
HOOC HS \0/---,, Br \0/'_ Br Blolljo BjoHIo
We thank RUSSIan Foundation for Basic Research (GR NN 02-03-32191) for financial support.
70 CA-16 RU0410054
NEW ADVANCES IN MACROPOLYHEDRAL BORON-CONTAINING CLUSTER CHEMISTRY
John D Kennedy, Mark Thorriton-Pett, Colin A Kilner, Jonathan BOUld, and Michael G S Londesborough.
Department of Chemistry qj'the University of Leeds, Leeds LS2 9T UK, e-mail: michae11 chem.1eeds.ac.uk
The rich and fertile chemistry of the polyhedral boranes is strongly manifested in the study and manipulation of single-cluster borane species. Less work, however, has been directed towards the expansion of its chemistry beyond its ostensible icosahedral limit. For this extension to be achieved, methods by which individual single clusters are linked or ised together to engender larger 'macropolyhedral' species must be discovered or designed. The homofusion of arachno nine-vertex cluster species provides one route to such macropolyhedral species 12,3]. In this context, the propensity of ara(-hno-[LMBSHj_,] metallaboranes to fuse and en-ender new macropolyhedral species has been investigated further. New results are reported', ad the structural nature of several new species are discussed along with possible insights into their fori-nation.
C :Ali
4,
%
1. M.A. Beckett, J.E. Crook, N.N. Greenwood, J.D. Kennedy, J. Chem. Soc., Dalton Truns. (1986) 1879. 2. P. Kaur, J. Holub, N.P. Rath, J. Bould, L. Barton, B. Stibr, J.D. Kennedy J Che,'n Sc., Chem. Commun. 1996) 273. 3. M.G.S. Londesboroug h,_-C.A -Kilner, M. Thornton-Pett, J.D. Kennedy, J rganotnet. Chem. 2002) in press.
7 CB-16 RU0410055
STUDIES ON NEW BORON COMPLEXES OF BIOLOGICALLY ACTIVE LIGANDS
Viiay P. Singlil ad R. V. Sin-h 2
Department of Sciences, Molcpolole College, University of Botswana), Private Bac, 008, Molepolole, Botswana.
Dej)artn1C17tOf Cheinistri-, LTniversitv qfRajasihan, daipla-302004, India, e-inail: ipsiyjwal(q yahoo.com
Several bolo-icallv active 112ands ere snthesized bv the condensation of aliphatic,
aromatic and heicrocvclic aldehvdes and ketones with livdi-azinecarboxamide,
livc1razinecarbothloarrilde. 2mercaptoarilline and sulfa du-s. These i-nonobasic bdentate,
dibasic tridentate and dbasic tetradentate lpands NNere used to synthesize boron complexes by
reactin tem In 1 I and 1 2 molar ratio with a variety of reactive boron compounds such as;
oxv(bis) dacetoxy borane, phenyld1hydroxy borane [1], '_-isopropoxybenzo-1,3-dioxa-2-
borol ad 2sopropoxybenzo-l, ')-thiaza-2-borole 2].
The resulting products were caracterized on te bsis of clernental aalysis and R, IH NMR,
C NMR. B NMR ad electronic spectral studies and tctraco-ordiiiated environment was
confirmed around boron atom in majority of te complexes. The onomeric nature ad non-
electrolytic behavior of the products as observed by molecular weight determination and
conductance easurements, respectively.
The bological activity of sorne of the representative laands and their boron complexes was
compared by testing their gromb inhibiting power against a number for bacteria and fungi.
This screening dernonstrated an increased atimicrobial activity of the corn Plexes over the IlQands that is an interesting and encouraging study of boron complexes.
The investigators are willinp- to share these findings with the world community of boron
chemists for feedback and further extension of such studies.
1. V. P. Singh, R. V. Singh and J. P. Tandon J Inorg. Biochem. 1990, 39, 237 - 245.
2. T. Pandey, V. P. Singh and R. V. Sngh, Main Group Metal Chem- 1999, 22 3), 315 -
320.
7 2 [A-12 RU0410056 MOLECULAR AND POLYMERIC PRECURSORS TO BORON CARBI DE NANOFIBERS, NANOCYLINDERSAND NANOPOROUS CERAMICS
Mark J. Pender, Kersten M. Forsthoefel and Larry G. Sneddon
Department of Chemistry, University of Pennsylvania,Philadelphia, PA 19104-6323, USA, e-mail: Isneddon(a-)sas.upenn.edu
The development of efficient methods for the production of complex structural and electronic materials in usable forms with controlled structures, orders and porosities is one of the most important problems of modem solid-state chemistry and materials science. We report here our development of efficient routes to boron carbide narlostructured materials based on te use of newly designed polymeric, [C61J11B1oH131x, and molecular, 6,6-(CH,)6-(B1oH13)2, precursors in conjunction with nanoscale templating methods.
-CH2CH-
\(CH2)4 H H
_JX [CGHIIBIOH131. Melt infiltration or vacuum filtration of solutions of these precursors through porous alumina templates followed by pyrolysis and dissolution of te meillbranes in 48% HF provide routes to boron carbide nanofibers and nanocylinders. SE%.l --and TE Vl analyses showed these methods yield aligned. monodispersed ensembles of materials. Structural control of the end products can be achieved through changes in concentration ofthe precursor solution, the nmber of alumina membrane treatments, and/or pore size of the alumina template. Nanoporous boron carbide atrices were enerated by employing ordered arrays of macroscale silica spheres as tmplates. The open spaces i these templates were first filled with te 6,6'-(CH2)6-(131(H11)2 reCLirsor by immersion in a mlt of te compound. Pyrolysis of te filled bodv, followed bv etchim, of te silica sheres from tile atrix by treatment with 8% HF, resulted in tile formation of oley boron-carbide frameworks Nvith ordered 50 nrn pores.
73 IB 12 11,11 I 1 1 II[ 11111 111 111 'll 1 RU0410057
REARRANGEMENTS IN THE NONA- AND NONAAZABORANE CLUSTERS
Mohamed El-Zaria, Udo D6rfler, Detlcf Gabel
Department of Cheniiso),-, University of Bremen, Gerinany
In the transition of (MeS)B,)H]3 t [(RHN)B8HjNHRj, one boron atom is lost. -
substituted derivatives of Me2S)B,)HI3 were used to identify this boron atom wich was
identified as being firi-niv ntegrated in the starting cluster. A pathway for the CDversion
is proposed.
H1. H R B RH2N B- H N B H H B B H H B B B RNH2 3.0 equiv) H B B + H3g NH2R B
74 [A-13 RU0410058 REACTIONS OF SILYL-0-CARBORANES WITH TRANSITION-METAL
COMPLEXES: FORMATION OF STABLE TRANSITION-M ETAL Si LYL
COMPLEXES
Young-Joo Lee, Seung-Won Chung, Sung-Joon Kim, Jaejung Ko, and Sant, Ook qng
Department of Chemistry, Korea Universi y, 208 Seochana, Chochilvon, Chung-nain 339- 700,
Korea, e-mail: sangok korea.ac.kr
Oxidative addition of S-H and Si-Si bonds to coordinatively unsaturated transition metal complexes is one of most useful methods for the formation of metal-silicon bonds. Stable metal silyl complexes are formed with a great variety of metal complex fragnents, and complexes of these types are intermediates in the catalytic hydrosilylation of nsaturated compounds. In particular, cyclic metal slyl complexes have been implicated as key interniedlates in the metal catalyzed double silylation of alkynes, alkenes, nitrites, ketones, and aldehydes. However, the intermediates have not been isolated due to their instability.
Thus, our interest has focused on examples of reactions of hydrosilanes Nvith metal complexes that gave isolated, stable syl-metal derivatives. The factors that promote the formation of a stable (solable) silicon-metal complex from the viewpoint of the substituents on tile silicon precursor also have not been systematically evaluated athou(gh electron-withdrawing roups seem to favor an oxidative addition reaction wth metal complexes from groupS 7- 1 I As part of our continuing program towards extending the versatility of metal sy cmplexes. bis(gen-nyl)nlckel complexes has been prepared. In this presentation. vve describe our recent study on the double slylation and germylation by nickel, palladium, and platinum cOrnplexes
[2].
L L L L L "' kM 101 -* M H M
R2Si N-1S iR2 R2Si "VI PR2 R2SiI SiR2 H, R2Si SiMe2
1. Ko, J.; Kan-, S. 0. Adv 01ganomet. Chem. 2001, 47, 61.
2. Lee, J.-H.; Ko, J.; Kang, S. 0. Cooril. Chem. Rev. 2002, in press.
75 B
cl -
ABSTRACTS FOR POSTERS P-1 RU0410059
A CONVENIENT PEPARATION OF TWO WEAKLY COORDINATINGANIONS OF THE CLOSO-MONOCARBABORANE SERIES
Jaroslav Ba&ovsk B. Stibr and J. P16ek
Institute f Inorganic Chemistry Academy of Sciences of the Czech Republic (Reseal-ch Centrefor New Iorganic Compoundy and Advanced Materials, Uiversity of'Pal-dubice), 250 68 he , Czech Republic, e-mail:jback Ccviic. cas.cz
The monocarbaborane an-Ion CB,)H14 is a very useful synthon for preparation of the weakly coordinating anions closo-CBgHg - and CB9H10 . The first synthesis of the C139H14 anion was published by Brellochs [1] and reinvestigated by our group 2 A simple preparation of the CB9H14 anion is based on the reaction of decaborane with formaldehyde ill an alkaline aqueous solution at O' C. After a short time it is possible to Isolate the alkali salts of the CB9H14_ anion, from which te tetramethylammonium, tetraethylammonium and tetrapheny1fosfonium salts can be obtained by simple metatheses. When these salts are heated in vacuum at temperatures over 200 'C, the salts of the respective coso-monocarbaborane anions are obtained.
The pyrolysis of Me4NCBL)H[4 gves a mixture Of Me4NCBsH,) and Me4NCBoH,( in molar ratio 2 I estimated from integrated "B NMR) in 64 yield. Wth the Et4NCB,)Hl,. salt the same treatment leads to both anions in molar ratio ' : I in 96 ,'o yeld, and prolysis of
Ph4CB9H 14 affords exclusively the C BxH9- anion in te same yield.
The support from the Ministry of Education of the Czech Republic Pect LN 0OA028 is appreciated. We are also indebted to 1. Cisafovd (Charles University. Prague) for the Xray structure of the CB,.)H t -anion.
1. B. Brellochs in Contemporai-i"Bot-on Chemisti-v, (Eds.:M.G. Davidson, A.K. Hughes, T.B.
Marder, K. Wade), Royal Society of Chemisty, Cambridge, 2000, pp. 2 22 14.
2. T. Jelinek, B. kbr, J. Holub, M. Bakardjiev, D. Hnyk, D.L. Ormsby, C. A. Kner M.
Thorn-Pett, H.-J. Schanz, B. 1N'rackmayer, J. D. Kennedy, Chem. Cmin., 2001, 756-1757
79 P-2 I 1 $ HI 1 11111 1 1 11 RU0410060 11-VERTEX PHOSPHACARBABORANE CHEIMISTRY.THE PREPARATION OF SOME HALOGENDERIVATIVES OF ni(lo-7,8,9,1 -P2C2B7Hq AND izido-7,8,1 I PC2138H I
Mario Bakardiiev, Josef Holub and Bohurnil tibr
Institute ofInorganic Cheniistiy, Acadenn, fSciences ofthe Czech Republic, 250 68, he near Pi-ague, the Cech Republic, Research Centrefor New 17ol-gallic Coinpounds and,4dvancedillaterials. Univei-sity of Par(lubice, e-inaik inai-io iic.cas.cz
The reaction of indo-7.8,9, I PIC2B-,Hg 11 and CC1.4 in the presence of AICI-, ave a mixture
J . 4:) of mono- and dsubstituted derivatives 0-C1-nido-1.8.9.11-PCB-H8 and 5,10-0,-nitlo- 7.8.9A1-PCB-H7. The reaction between nido-7,8,9.l1-PCB7H" and elemental oine in benzene. using the AIC13 catalyst, led to thelO-I-iiido-'/,8,9.11-P2C2B-7HS and 5,1042-nido- 7.8,9 1 1-PCB7H7 derivatives. Bromination methods (Br /A]Br,,; A]Br-/CS,; CHBr3/AlBr3;
CBr4 '.-%IBr-) led, however, to the decomposition of i7ido-7,8,9,1 I PCBHc) Sccessful was the brornination via reaction with N-broi-nosuccinimide M CHC12 ging a mixture of 3-Br- nido-7,8,9,1 I P2CB7H8 and 2,3-Br,-nitlo-7,8,9,1 I P2CB7H7. Similar reactions were also made with thenido-7,8,1 -PCBJl11 phosphacarbaborane 2]. Individual compounds were characterized by ass spectroscopy and multinuclear (13, 1H and P) spectroscopy combined with two-dimensional ['' 13- ' B]-COSY NMR techniques[3]. This work was supported by the Mnistry of Education of Czech Republic (project no. LNOOA028). We also thank Drs. J. Fusek and Z. Pz k for NMR measurements and ass spectra.
1. olub J., Jelinek T., Hnyk D., PlzAk Z., Cisafovd L, Bakardjiev M., Stibr B.: Chem-Eur.J. 7, 1546 2001). 2. olub J., Ormsby D. L., Kennedy J. D., Greati-ex R., tibr B.: norg. Chem. Commun 3, 178 2000). 3. fiolubJ.,BakardjievM.,StibrB.:Collect.Czech.Cheni.Commun.,inpress.
80 P-3 RU0410061
BORONATES CONTAINING FERROCENE UNITS
Victor Barba. Norberto Farfdn and Rosa Santillan
Departanzento de Quimica, LIV VESTA V-1PN. Apdo. Postal 14- 740, 07000,Wxico D. F, Wxico, e-mail: harba73Cahotmuil. com, jax 52(55) 74 771 3
The syntheses of compounds with ferrocene units have attracted considerable interest in te last two decades due to potential application in electronics [1]. Very recently e have described the formation of macrocyclic compounds from the reaction of Schiff bases with arylboronic acids 2,3]. Herein we report the synthesis of boron complexes derived from ferroceneboronic acids and
tri -itate ligands. The results show that ligands with to C112 groups between the OH and N=C groups lead to dimeric compounds (la-1c), however, the presence of a bulky group
attached to the nitrogen atom favors fon-nation of monomeric complexes having tvo boron
atoms (2a-2b), one with tetrahedral and the other one with trigonal geometry. In addition,
bicyclic structures were obtained from the reaction of ferroceneboronic acid with a tridentate
ligand derived from 4-aminobutanol (3a-3b).
R R R
N 0 N N i 0 B -B 0 0--j
FIe re Fe Fe
la: R=H, lb: =Me, le: =Ph la: R=H, 2b: R=Nfe 3a: R=H. 3b: =Me
These boron complexes were obtained in good yields 0-90 9'0) and were fully characterized by spectroscopic techniques. The structures of la and 3b were established by Xray diffraction which show that the boron atom is tetracoordinated and the feFrocene nits arcal7ti in la.
-I.-A. To",i, 1'. Hayashi, Fei-i-ocenes, VCH Weinheirn. Germany. 1995.
2. N. Farffin H 116pfl, V. Barba, M. E. Ochoa, R. Santillan, E. G6mez, A. GLItierrez, J
Organomet. Chem. 581 1999) 70.
3. V. Barba, E. Gallegos, R. Santillan, N. FarfiinJ Oi-ganomet. Chem. 622 2001) 259.
81 P-4 RU0410062
FORMATION OF BIMETALLABORANES USING RHODATHIABORANE OR RHODADICARBABORANE TEMPLATES
Oleg Volkov, Nigam P. Rath and awrence Barton
Department of Cheinistij,, University ofMissouri-St. Louis, St. ouis, MO 63121, USA e- niail: 1barton ums1.edu
The phosphine lgands on [8,8-(PPh3)2-iiido-8,7-R-hSBgHlo] (1) and [9.9-(PPh3),-nido-9,7,8-
RhCB8H I] 2) may be replaced by the bidentate phosphine, [(CH,) (PPh,)-] (dppm) to form
the species [8,8-(Tl -dppm)-S-(91-dppm)-t7ido-8.7-R]iSB,)Hlo 3 and [9.9-(ij2-dppm)-9-('q'-
dpprn)-nido-9,7,8-RhCB8Hjj 4 This paper will describe the fori-nation of a series of
bimetallaboranes based on 3 and 4 For example 3 reacts wth [Ru(q 6-P-CYM)CI.12 to afford
[8.8-q 1,(p-Cl)-Ru(11 6-p-cyiii)(dppm)'-izido-8,7-RhSBgHl(jI (5), which contains the group
[(p-C1)-Ru(q'-p-cym)(dppm)] that coordinates in a multidentate mode to Rh. Similar
chemistry based on species 4 is also observed. Reaction of 3 with [Cp*IrCI212 tCP*
[C ;(CH3)51 affords the related species [8,8-q 2_ (VL-Cl)?Ir(q5_Cp*)(dppi-n)l-i7i,,Io-8,7-
RhSB,)Hjuj 6) and reaction of I with [(ill-dpprn)Cp*RhC12] affords [8,8-ij2_ j(V-Cl)2Rh(,q5_
Cp*)(dppi-n)l-izido-8,7-RhSBgHlo] 7). Reaction between I and 3 affords the novel species[l-
PPh3-5,1,3-(p-dppm),-closo-1,2-RhSB9H8] (8), which when treated with (CH2)2(PPh2)2,
(dppe) gives [ 1 _112 -dppe)-3-(ill-dppm)-closo-1,2-R-hSBgHg] 9). With [Ru(Tl6_P_CYn1)Cl212,
9 affords the closo-systern [1,1-(TI 2-dppe)-3- (ij'-dppm-Ru)(q6_P_Cym)C 12)1 ClOSO- 1,2-
RhSB9H8] (10), in which the rhodathiaborane cage has a pendent metal-]]gated dppm group at
the 3-position. Species 3 reacts with [ClRh(PP]13)31 to afford which on further reaction
gives the unusual species [8-Cl- 8,9(p-dpprn) I -PPh3-11ido-8,7-RhSBqH71 (II).
82 P-5 RU0410063 UNUSUAL STRUCTURES OF RHODIUM BORYL HYDRIDE COMPLEXES
A.S. Batsanov,'J.A. Cowan,'J.A.K. Howard,'T.B. Mardcr,' S. Shirnada, 'S.A. Mason,' G.J. Mcfntyreb W.H. Larri'and Z. Lin'
aDept. of Chemistr-v, University of Durham, Durham DIH 3LE, U. K, e-niaik a.s.batsanov durhani. ac. uk., bInstitut Laue Langevin, Gi-enoble, France,`Dept.of Chemistry, Hong Kong Universi y of Science and Technology
Complexes [(Pr i3P)2RhHCIXI, where X = pinacolboryl (1) and catecholbory 2 important for their role in metal-catalysed hydroboration of unsaturated organic substrates, have been studied by single-crystal X-ray diffraction at 120 K [I] and neutron diffraction at 2 K. Both complexes have trigonal-bipyramidal coordination with axial phosphine ligands, with strongly and unusually distorted equatorial angles. Although the coordination plane of te atom is close to the equatorial plane of the bpyramid in 2 and nearly perpendicular to it in I (Figure), in both cases the H-Rh-B angle is very acute. Ab initio calculations using the Natural Bond Orbital analysis indicated a substantial H ... B bonding with Wiberg bond indices of 0.18 (1) and 015 2 while those for the Rh-B bond equal 0.80 (1) and 0.8 2 In 1, the Rh-H bonding orbital overlaps with the p(-c*) orbital of the atom, in 2 it overlaps ,kIth the * orbital of the B-0 bond. The implications for the reactivity of the complexes are discussed.
01 H H U Rh Rh B 01 B C1
P2 P
Neutron structures of I (left) and 2 (right) at 20 K 50% thermal ellipsoids). Dstances (I ad 2, resp., A): Rh-II 1567(5) and 1.53(l), R-B 1983(4) and 1973(7); angles (): H-Rh-13 67.8(2) and 68.5(4), H-Rh-Cl 17' ).5(2) and 152.6(4), B-Rh-Cl II 8.7(l) and 138.8(3).
1. S. Shimada, A.S. Batsanov, J.A.K. Hovvard, T.B. Marder, Angew. Chem. Int. Ed. Engl., 2001,40,2168.
83 P-6 RU0410064 SYNTHESIS OF FUNCTIONALIZED SCHIFF BASES AND BENZYLAMINES DERIVED FROM
THE coso-DECABORATE ANION 1131 OH1012-
Vikentii Bragin, I-orZ_ Svaev, Natal'ya Votinova, Vladimir Bre-adze, Stefan S'bberg
A. N A esnievanov Institute of Organoelenient Conipoun(ls, Russian A adem-1, Qf Sciences M. V. Lonzonosovlfoscoiv Institutc.foi- Fine Chemical Technology Depanniew of Organic Chemiso-i-, Institute Chemistry, ( Ppsala Univel-sity
Recentiv e have dex eloped a nw approach for synthesis of functional derivatives of the
closo-dodecaborate anion [B12H !,]2 ' based on the reaction of its arnino derivative
[Bj-HjjNH-]- with aldehydes followed by reduction of the formed Schiff bases []. The
functional derivatives prepared can be used in boron eutron capture therapy or as fin-ers for
attachment of radioactive halo! en labels to onoclonal antibodies 2].
In this contribution we report synthesis of Schiff bases ad substituted benzy1amines
der]Ned from te closo-decaborate anion [Bl(Hio] Two isomeric series of derivatives
containing substituents at the apical and equatorial boron atorns of the closo-decaborate cage
wcre prepared.
R7 R-1
7_ 10 Nit, C "2N H,
0 R4 H
72- Meoll %Icl
Hc R H24C_0 R
NH3 0 Nil Nlf2 R4 NaB114 MeOlloil- r 4
R (,11., Q1,-2-ONle, li,-4-NHCOie
This work was supported by INTAS 99-00806), the Russian Foundation for Basic Research
(02-03-32 192), and the Swedish Cancer Foundation.
1. I.B.Sivaev. A.B.Bruskin, V.V.Nesterov, M.Yu.Antipin, V.I.Bregadze, S.Sj6berg Inorg.
Chem., 1999, 38, 5887,
V.Tolrnachev, I.Sivacv, A.Bruskin, S.Sj(5bcrgEur, J. Nucl. Med., 2000, 27 1062.
84 P-7 RU0410065
SYNTHESIS, STRUCTURE AND DYNAMIC BEHAVIOR IN SLUTIO OF
NOVEL exo-nido-OSMACARBOR.XNE DRIVED FROM Inido-7,9-C,139" 1 12-
Dmitrii N. Cheredilin, Elena V. Balagurova, Fedor M. Dolgushin, Oleg L. Tok, frina G. Barakovskaya and Igor T. Chizhevsky
A.N. Nesineyanov Institute of Organoelement Compounds, 28 Vavilov Str., 119991 luoscow, Russia, e-mail: chizbor ineos.ac.ru
Novel 16-electron evo-nido-osmacarborane, exo-nido I 0 I I 1(Ph3P)2H20S1 I 0 I I (p-H)2-7,9- I -K+ and (PPh C21391-19 (1), was obtained from the reaction of [nido-7,9-C21391-1121 3)30SCII in ethanol. An essentially noteworthy feature of this complex is the presence f only two 13- H ... Os bridges linking te metal-containing moiety with the nido-carborane igand. Both bridging hydrogen atoms are attached to the boron atoms of the open pentagonal face of the carborane cage. The structure of this complex has been clearly confirmed by means of NMR and single crystal X-ray diffraction studies.
(2)
Based on the temperature dependent H and 31 P NMR spectra te fluxional behavior of complex in solution has been revealed. Besides., the dynamic NMR experiments showed that exo-nido-osmacarborane I pon heating in ds-THF-solution could be nonreVeTSibly rearranged into closo-isorner of 1, closo-2,2-(PI13P)-)-2,2-H,-2,1,7-OSC2B,)HI 2). The quantitative conversion of I into 2 as been achieved v thermal reaction ad te structure of 2 ws confirmod by a X-ray dffraction study. This research was supported by te Russian Found3tion for Bsic Research Grant No 00-03- 32824). 85 P-8 RU0410066
NE'"' IZESULTS IN THE CHEIN11STRY OF TE BORON SBHAIADE CLUSTERS
Wolfgan(_ Einholz, Daniela Gl nzel, Kut Vaas, Christoph Wieloch
Instinifflir Chemic, Unive)-sildt Hohenheini D70593 Stuttgart. Gel-mally, e-niaik einholz( ' i uni-hohenhcim.de
III continuation Of OLE- Studies of te boron subhalide lusters, we investigated different reactions
of BX14, B,,C],, (n 9 ad [BjoXj(j2_ (X = Cl, Br).The reduction of B4C14 with [Bu4N]l 1:2)
does not iead to the canion FB., C, _,]2 - but t velds the 8-vertex cluster c1oso-[B8Cl8]2- Opposite to som rports 'In erature, BsCls. hich as sublimed in thevacuum line, does not ha\ a ed or purple ccdor bu tin avers of BsC4 are dafK c_,ree wereas tick lavers appear ncarlv black. However, te hydrolysis product of BCls is intensively purple-colored. This
li drolvsis product is formed already With traces of hurrildlo,' or In solvenis wich were not dried
verv Well. According to te ESR spectra and to the electroanalytical nestigation (cyclic
Noltamnietry, chronocoulometry). this hydrolysis product contains te radical aion hypercloso- 11380 1_ [1] Ts result is also confin-ned by the comparison with [B, ,Clg]- which was
sNiithesized b the rcducuion of BCl, vith [Bu4N]l or [Ph4P]1 in a olar ratio of 1: 1. In contrast to te results of Morrison and his coworkers 2], We did not observe any reaction of B, 08 with Ure and \,Nell dried pentane or dichlorornethane wch does not contain ay stabilizing agents like pentene or hexene. However, if traces of these stabilizing agents are present the radical anion [BsCls - is formed. Te dianion c1oso-[BgClg]_ can be obtained by te
reduction of B808 With [Bu4N]l or [Ph4P]l in a molar ratio of 1:2. According to the single-
cr,,stal X-ray diffraction study, [B8CI8] 2- adopts a dodecahedral structure with narly D2d
symmetry [. Str6bele, H.J Myer, Univ. Tilbingen]. However, the B NMR spectra of
solutions of [B, C]81 2- show 011v one signal indicating the fast fluctuation of this closo-cluster.
The moleCUlar structure Of CS2[BjOBrjO] 2 HO was determined by X-ray diffraction. Closo-
[BI(Br, O]2- has a bcapped square antiprismatic structure with (nearly) D4d syrnmetry. [B JOC110]2-
can be oxidized by T(CF3C00)3 to the stable radical anion hi, ei-closo-[BI(C 10] -. The redox.
system [B I OX I 21 1 X C Br) was investigated by electroanalytical methods (CV, CC) 3].
1. B. Speiser, C. Tittel, W. Enholz, R. Schdfer, J. Cheni. Soc.. Dahon Truns. 999, 1741.
2. J. A. Morrison, 717cm. Rei,,. 1991 9, 35.
3 W Elnholz, K. Vaas, C. Wieloch, B. Speiser, T. Wzemann, M. Str6bele, H-J. Meyer,
Z. Anoi u. A1g. Chen-i. 1-002, 628, 258.
86 P-9 RU0410067
PALLADIUM-CATALYSED HECK REACTIONS OF STYRENE DERIVATIVES WITH 2-1-P-CARBORANE
Ludvig Eriksso Karl Johan Winberg and, Rodrigo Tascon
Department of Organic Chemistry, Institute of Chemistry, Uppsala Universi v, P.O. ox 531, S-751 21 Uppsala, Sweden. Einail: ss/Cq-,kemi.uu.se
We ave recently shown that the boron iodinated 2-I-p-carborane reacts with arylboronic acids under mild Suzuki-Miyaura reaction conditions to form 2-carboranyl arenes in hh yields [I]. I this contribution we show that 24- p-Carborane also can be used it] the Heck reaction. Thus the reaction between 2-1-p-carborane and styrene and various Sbstituted styrenes [4-C6114-, 4-Cl-, 4-Br-, 4NO2-, 4-CH30- and 4-013-1, gave the corresponding trans- 8-(2-B-p-carboranyl) styren in DMF solution when reacted in the presence of slver posphate and the palladacycle Herrmann's catalyst 2], 3] (Fig. I).
Ar
Ar Pdbase + 30 DMF
0 =CH 0 =B/BH Fig. 1: 2-1-p-carborane applied in the Hck reaction with styrene and various stvrene- derivatives.
This work was supported by the Swedish Cancer Foundation and b NLTAS 99-00806) in the frame of a collaboration on Pd-catalvzed reactions with Profs. I.P.Beletskava. A. Bre(yadze. and S. Sj6berg.
1. Eriksson, L.; Beletskava, 1. P.: Bregadze, V. I.; Sivaev, 1. B.; Sj6ber,-,. S..J. Oruanomet. Chem. 2002, in press 2. errmann, W. A.; Beller, M.; Fischer, I-I.; Ofele, K.; Brossmer, C.Angew. Chem. nt. Ed. Fngl. 1995, 34, 1848-1849. 3. Herrmann, W. A.; B6hrn, V. . W.; Reisinger, C.-P. J Organoinet. Chem. 1999, 76, 23- 41.
87 P-10 RU0410068 COMPLEXATION OF 13i2111212 AND [B,,Ii,,SCN,2 ANIONS WITH CYCLIC TRIAIERIC PERFLUORO-0-PFIENYLENENIERCURY
A.M. Filin, M. Tugashov, I.A. Tikhonova, F.M. Dolaushin, M.Yu. Antipin, ].B. Sivaev, L.N. Teplitskaya, E.V. Bakhrnutova, V.I. Bregadze, L.M. Epstein, V.B. Shur, E.S. Shubina
.4.A'. Nesmevanoi, Institute of Oli-guanoelement Compounds, Russian,4cademy ofSciences, I'avilov Sr 2,119991 Moscow. RUSS1.4. E-nial'l.'_flli77Caiiieos.ac.1-u
Interaction of [Bl2H,-]-' and [13121-111SCN1- anions with cvcI]c tridentate ewis acid (o- C,,F-4H,-,)-- has been studied. It has been sown tat te anions form in solution complexes of two different ty I 2 k ]2- 1 pes - [(o-C(,F4Hg);][A] - and [O-C6F4Hg)312[A] (where A is [B :.H]2 ]2-). N or [Bl2H,,SCN 101 ecular structures of (BLi4N'),,[(o-C6F4Hg)31,)[B]2H,,]I () and
(BU4N)2 [(O-C6F4Hg)-]2[Blli,,SCN] 2 have been determined by single crystal X-ray
diffracilon. Both complexes have tilted sandAlch structures with the boron hydride anions
located between the planes of two macrocycle olecules ad bonded to each of thern via the
1341-1-1g bridges of to types ith participation all tree and only one mercury aom) In
structure 2 t boron hydride anion is rotated inside the macrocyclic jaws by te thiocyanate
substituem formin- an additional H--S-Hg bridge.
F(5A) 1`112)A Ml MI F115A) A) FQAi hq(2A) Cfl4l Hit Cf7A Al A) Al H(4 MD
F .1 H H9A) F1171 HIM
r(Gal F1331 FQ F115B) F(34J e 1491 F(SB' H 2AI )F(17B)
F138,
C
F 2 FUN I'MIN FMOB)
This wort. was supported b te Russian Foundation for Basic Research (the Project
codes 0 1 03-32068, 02-03-33304, 02-03-06243, 02-03-06388).
88 P- I
RU0410069
RADIO[ODINATION OF 13-AMONIOPROPYL)-7,8-DICARB.,k-iV/DO- UNDECABORkTE(4) (ANQ
Senalt Ghirmaia, Jonas Malmqulsf', Hans Lundqvist h Vladimir Tolmacheva' b and Stefan Sj6berg '*.
aDepartment of Organic Chemistrv, Uppsala University, Box 53 1, S- 751 2 Uppsala, Sweden; bBiomedical Radiation Sciences, Uppsala Universin', Box 535, S-751 2 Uppsala, Sweden
The synthesis of racemic 7-(3-amonio-propyl) -7,8-dicarba-/ii(lo-undecaborate(- I (1, acronym ANQ has previously been reported by us [I]. We have used the amino function in I for conjugation'to tumour targeting macromolecules and te nido-cage as a prosthetic group for radioastatination and radiodination of the conjugates obtained. For a review of work in this area see 2]. In this contribution electrophilic lodinationiradio lodination (with 251) of racemic ANC will be described. Racernic ANC was radloiodinated (12 1) using the chloramine-T method to yield a nixture of two constitutionally isomeric pairs (rac-2 and rac-3). Radio-TLC results showed that radiolabelline,Z:1 with 125 1 was achieved in It,areater than 9711 O.
(CH2)3NH( 0
3 (CH2)3NH3 (CH2)3NH3
I+or 1251+ (CH2)3NH 3 (CH2)3N4D (CH2)3NF 1_)
rac-1 rac-2 rac-3
ic =BH =C o =CH
=H B1 or = 1251
This research has been supported byI te Carl Trygger ZD Fundation For Scientific Research. INTAS (grant 99-00806) and te Swedish Cancer Fundation.
1. J. Malmquist. Boronated Arnines and Aino Acids for Boron Neutron Capture Therapy. Acta-Utiii7ersitatis-Upsalleti, is. omprehensiie Summaries #'Uppsala Dissertationsfi'Mil the Faculty of Science ad Technology, 125 1995), ISBN 91-554-35 3 19. 2. V. Tohnachev and S. Sj6berg. Polyhedral Boron Cmpounds as Potential Linkers for Attachment of Radlohalogens to Targeting Proteins and Peptides. Accepted for publication in Collect. Czech. Clicin. Conimun_ 2002.
89 P-12 RU0410070
NOVELrINCARBORANECARBOXYLAI'ES SYNTHESIS, CIIARACTERIZATION AND IA'I 7TRO ANTITUNIOUR ACTIVITY
h bc S.A.Glazuri", V.I.Breaadze', Z.A.Starikova', P.V.Petrovskil', 1J.Dall] ,M.Bicscnians
b.c d b R.Willcm , D. de Vos ,M.Gielen
'A.N.Nestnevanov Istitute of Orgaimeleinent Compounds, Russian Academy of Sciences, 11 9991,,Woscow, Tavilov st. 28, Russian Federation,einail: gsaCqineos.ac.ru V'rije Universiteii Brussel, Pleinlaan 2 B- 10-50 Brussels, Belgium
Dej)arrincin of Generail and Organic ChOniSOT (.40SQ. Faculti, f.Applied Sciences
'Hiah RCS0111tiOn NWR Centre Vcdical Departmem. PCHNedcriand. Pharniachenzic B. 1'.. N1-2003 RV Haarlem, Ae Netherlands
A lot of tin derivatives exhibit promising 70-0 antitUrnour activities aainst some hurnan cancer cell lines [1]. Now we report the synthesis, characterization and i vitro anti I 11 tumour act v t es of sorne no el t'ncarboranecai-boxviates. A condensation of d1butyltin(W) oxide wth I,2-carborane-9-carboxylic acid (in 12 inolar ratio) resulted in d-1,2-carborane-9-
acetato-di-n-bUtVitin (1), the first carborane- B6'
based or-anotin compound where the oil CT carborane caccZ is linked to the carboxylic - VAzll _, - molct% via a boron atom.. Its structure was O' B ST detcrimned by spectroscopic and X-ray
diffraction methods. 07 The compound (1) screened i vitro against
sevell tunioural cell lines of uman are C9 ' ificant1v more active than 5-fluorouracil, ]-,n C10 cis-platin and carboplatin. C11
Table 1. In vitro antitumour activities (ng rril") against MCF-7 and EVSA-T, two breast cancer, IGROV. on ovarian cancer, M 19 MEL, a melanoma, A498 a renal cancer and H226 a non small cell lun cancer.of (I together those of some reference compounds used clinically. Compound MCF-7 EV A-T WiDr lGROVF _I9MEL A498 f 1226 1 146 142 439 139 174 195 291 Carboplatin 10500 4500 i 3500 2400 5500 1800 25000 Cis-platin 1400 920 1550 230 780 1200 3158 5-FiLlorouracil 350 720 440 850 310 340 5300 Methotrexate 15 2 6 7 20 16 70 I)oxorubicin 25 13 18 150 +21 55 180
This vork was supported by INTAS (grant 99-00806 ad RFBR (grant 02-03-32192).
M.Gielen, Coord. Chein. Rev., 1996, 151, 41.
90 P- 13 211111111H RU0410071 ESTER AND AMIDE CARBO[C-XNE DERIVATIVES OF SOME NATURAL AND SYNTHETIC PORPHYRIN'S.
R.P. Evstigneeva 1, V.N. Luzgina I A.Y. Gorshkov I P.S. Tmashev 1, P.V. Petrovsk''11-,
V.A. 01'shevskaya 2
M. V. Lomonosov Moscow State Academy of Fine Chemical TechnoloD,, 86 Pernudsky Pi-_ 11 75 71 Moscow, Russian Federation
2A.-Y. Nesmeyanov Institute of Organoelement Compounds, RitssianAcademv ? Scienc-cs, 28 Vavilova stj-., 11999]Moscow, Russian ederation
Increasina interest in new carboranylporphyrins as potential objects for medical research is due to the dvelopment of, e.g. boron neutron capture therapy of cancer. To search for effective compounds for this unique method we synthesized a number of carboranylporphyrins in which the carborane polyhedron is bonded to porphyrin through an ester and arnide bond. Using 2-(2-carboxyvinyl)-5,10,15,20-tetraphenylpoiThvrin 1) and 9-hydroxyrnethyl- in-carborane 2), 1-hydroxyniethyl-o-carborane 3) and 3-ai-nino-o-carborane 4) di-tert-bUtVl pyrocarbonate, as activating agent, new carboranylporphyrins 5-7 wre obtained.
Ph Ph 0 0\ Hol CCH=CH R. -CH= C II NH 0 - CHC], N Ph N HN Ph - -]I- Ph N HN Ph BocO. DMAP
H Ph 1. I C 6. R=R1 RI= R2= elA c - R3-1 4-/2A\' N - CH:-0_ 2 3
Based on deuteroporphyrin IX (8) and protoporphyrin X 9 and LISIncy the same activation ethod of carboxilic groups, and carborane derivatives 2,4) and 9-hydroxymethyl- o-carborane (10) some mono- and dcarboranyi-substituted porphyrins were obtained. This work was financially supported by the Russian Foundation for Basic Research grant X2 00-03-3287-2a and N2 00-15-97866.
91 P-14 RU0410072 STABILIZATION OF PLANAR TETRACOORDINATED NITROGEN IN ORGANOBORON COMPOUNDS
Tatyana N. Gribanova and Ruslan M. Minyaev
Institute of PhYsical ad Organic Cheinistril at Rostov State University 19412,4ve. Stachki, 344090 Rostov-on-Don Rssian Federation, e-niaik tnCqJpoc.rsu.ru Stabilization of lanar tetracoordinated nitropen atom in organoboron compounds of arious I - -
structural tpes has been studied b ab inirio (MP2(full)/6-31 +G**) and DT (B3LYP/6-
')II G**) ethods. Calculations predict stable structures of the nonclassical NBCH and
NBj compounds containing one and two planar tetracoordinated nitrogen centers,
respectively Tese neutral sstems are the first theoretically predicted examples of boron-
containing organic compounds with planar tetracoordinated nitrogen.
Some anionic systernsand the influence of the lithium counterion on their stability and
structural parameters were also investigated. Te N136' anion and two isomers of NBlfl4-
anion containing planar tetracoordinated nitrogen center in boron-environment, according to
calculations, correspond to minima on the relevant potential energy surfaces. Insignificant
influence of counterions on the stnictural characteristics of these planar anions suggests the
ibility of teir experimental detection.
Russian Foundation for Basic Research (Grant 01-03-32546) and NTAS (Grant 00-
00 1 79) have financial supported this work.
92 P- 15 RU0410073
SYNTHESIS OF POLYALLYLATED o-CARBORANES
V.A. 01'shevskaya. M.A. Guil'malieva, PV. Petrovskii, !F.V. Pastukh-o and Yu. N. BLIbnov
A. N. Nesmeyanov Istitute of Organoelement Compounds, Rssian Academ1v of Sciences, 28 Vavilova str., 119991 Moscow, Russian Fedei-ation.
Allylic boron compounds are widely used in organic chemistry as useful synthons for further functionalisation of substrates.
Various mono-, di-, tri-, and tetraallylated o-carborane derivatives were obtained usingZ1- three general approaches for the C-C and C-B bonds fori-nation: - low temperature boron insertion of allylboron fragment into nido-precusor to furnish closo-systern; - Pd-catalyzed cross-coupling of odocarboranes with ally1magnesiumz:1 chloride-, - interaction of C-11thiocarboranes with allyl bromide.
H H 'C C R3-6 HC CS- 012=CII-CH21302 3-R3 R 1-5 THF C'[i2-CH=C11-)-3 12-RI
I-112 9-R2
I RI=H. R2=I4,R3=-C112-CI1=C[1_-) IV RI=H.R2_F1-R3=-CH1-C1]-C11__) 11 R1=1. R2=1-1. R3=11 V RI=!.R2-1-LR3=H III RI L R3=1, R3=11 VI RI =. R3=1, 113 I
H H C CH,-CH-C11,WC1' C (Ph,P),Pd C, C1 I-CH 01 FIT CH-CH-01,-1 -)-CH,-CH-CH' F
12-R I 1-R V11 RH IX R=H VIII R-1 X R-CH)-CH=CH,
H CHZ-CH=C1i,
I 2BuLi -CF12-CH-CH, 2) C1-1-CH-C[1,Br 9-CH-CH- 2 9-CH2--CH-C1- 12-R 12-k
Xi R=11 X111 R H X11 R 01-CH-CH2 XIV R=-CH2-CF1-('H. Tri- and tetralodo-iiido-7,8-dicarbaundecaborates as starting compounds for the preparation of polyallylated carborane derivatives were also synthesized. Structure of all compounds obtained was confirmed by 11 ad B NMR spectra.
93 P-16 RU0410074
ELECTROPHYLIC AMINATION OF BORACYCLANES WI'-J1'1-1 HYDROXYLANIINE-0-SULFONIC ACID
M. E. Gurskii', D.G. Pershin", Yu. N. Bub,,OVb
N. D. Zelinski, Institute of Oi-ganic Chemisoy, Russian Acaciemy ofSciences, 119991, GSP-1, Leninskypi-osp- 47, Afoscow. Russia. E-mai1ho1-Ctvcac1-.ioc.ac.ru Institutc of Oi- noclemel7tCoinpounds, Russian.4cademv of Sciences, 4.A'. Ncsincvanoi .a
11 9991. 'avilova sti-., 24, Moscow, Russia.
Ammoalcol ols 3a.b were s-y-ntliesised bv amination of bicyclic boranes 2 and 4 with
N11,0SO-1-1 (1) followed bN 7oxidation of reaction mixtures by alkaline hydrogen peroxide.
Similarly, 2oraadamantane 5 as transformed into b1cylo[3).3).1]nonane 6 Migration
Utilities of intracyclic boron-bound alkyl oieties in triorganylborarie 4 and are found to be
5-10 iii-nes h1oher tan those of methyl and sopropyl groups.
Ome 13 RI RI -"["000 iN1 , JI W. 650C I. Z 1-IF. 650C 2ab 5 oil 2. Na0I . O' 2. Na0I 1 I , C'I M I I 2 - 6:35%; 3ab: I I(a). 20%: Me(b). 45% NI IOSOH
N." C I INH, Me OMe R- CHNI 1, R I. THE 65'C CI W I 4 7ab CH 2OH 3b: 30%: 2. NaO I 1120, 2. NaOH. 1,0, 8ab; R = f a), 30%; C1 120CH3(b), 20,
Mixtures of isomers 8ab dffering in double bond location, were isolated frorn the
reaction of 3-borabicyclo[3.3.1 ]non-6-enes 7ab.
This work was supported by Russian Foundation for Basic Research (Grants 01-03-
32405, 00-15-97378 and 02-03-32249).
94 P-17 RU0410075
SYNTHESIS AND CRYSTAL STRUCTURE Fconjuncto-3,3'(1.2-PB4BR3)2
Willi Keller, Gisela Sawltzki, and WolfgariL Haubold
Institut Nr Chernie, Universltdt Hohenheim D70599 Stuttgart,
e-mail: kellerw OLuni-hohenhelm.de
We previously reported heteroboranes of the elemental compositions E13806 (E = P, As) 1,
2] as minor products of the copyrolyses reactions of BC14 with PC13 or AsC13 and proposed boron-boron linked structures (E21340_302 for both compounds. These studies prompted our reinvestigation of the bromine analogous copyrolysis reactions as a means of obtaining linked-cage systems appropriate for separation ad crystallization. In tis poster, we report the synthesis and crystal structure of coiijitiic-to-3,3'(I.'- -PB-,Br3)2 which represents the first polyhedral multicage phosphaborane borane proved by a single-crystal X-ray sudy.
Pi 6'
5 4-N
6
1. Keller, W.; Sawitzki, G.; Haubold, W. Inora.el Cheni., 2000, 39, 1282-1287.
2. Enholz, W.; Sch5fer, R.; Keller, W- Vogler, B. Z. Nalutforsch. 1997, 52 b 21-226.
95 P-18 111 1[ 11 1 1 1 1111 1 11 RU0410076
NOVEL C-BRIDGED BISBORONATE DERIVATIVES BYINSERTION OF DIAZOALKANES INTO BIS(PINACOLAT0)DII30FLkNE(4).
Miazi Abu Aand orris Srcbnik' Depai-tinent of Medicinal Cheinisti-i ad A'aan-al PI-oducts, School qf Phai-macv, Hebrew L"niversitv in Jerusalein, Je)-usalenz, JS7-ael, e-inaik insi-eb a 7d.ht i.ac.d
The ain LH-POSe of te ork is to synthesize B-C(Rj R,)-B compounds. Boronic esters and
their acids hve a varlev of important uses and applications [1]. They are hhlyI valued s,,nilietic ntemiediales and also possess sanificant biological activity [21. The insertion reaction of bs(pH,acoiato)d1borane(4) [(Mc4CO,)BB(OCMe4)- 1] with vanous dla7oalkalnes provided novel rpresentatives of a new class of substituted C-bridged b1s(pinaco1ato)d1borane(4) derivatives 5a, 5b, 5c and 5d in a range of 75-78% isolated yields. The reaction as efficiently catalyzed by Pt(PPh3)4 in tuene at II 'C. Single crvstal Xray dffraction, GCMS and NMR inultinuclear spectroscopy fully confirmed the structure and confiauration of the new compounds. Crystals of 5a and 5 ae centrosymnietric, while those of 5d are chiral. 5 cystallized wth a somewhat unusual d(12 space symmetry Wle its crystals are noncentrosyi-ni-netric, they contain tnirror-related species.
.6
23
T C22 C22
C2
C B2 0 C- C'2 0? C,
12 C, '_'r C'8 -03 11 5b 5d
1. Pelter, A.; Smith, K.; Brown, H.C. Boi-ane Reagents: In Bst Synihetic Methods; Katritzky, A.R.; Mleth-Cohn, M.; Rees, C.W. Eds.; Academic Press: London, 988. 2. Morin, C. Tti-ahedron 1994, 50, 12521, for a review of biologically active boron analogues. +H. A. A. acknowledaes a travel urant frorn the David R. Bloom Cnter for Parmacy at the I ebrew University.
96 P_ 19 I [ 1[ II 111[ 1[ t 11 11 RU0410077
STEREOCHEMISTRY OF NEWLY PREPARED CARBORANES AND PHOSPHABORANES
Drahornir f nyk and Bohurn I StIbr
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, CZ-250 68 REZ near Prague, Czech Republic, email: hnykCw iicxus. CZ, 2stibi-(Wiic.cas.c-
The molecular structures of so far missing" monocarboranes 121 Sch as C 1171 and [CB8H9] ad of a series of closo- and nido-N-vertex phosphaboranes (N 10,12), 34,5] III some cases icluding their C-derivatives, were determined by b initiolGIAOINM R method. The final level of geometry optimizations included the effect of electron correlation, which considerably improved the fit between the calculated (GIAO-SCF or GAO-MP2) and experimental B chemical shifts. Such a good agreement between 6(1 13)" ad ('' B)"" may serve as a criterion of the correctness of the molecular geometry calculated for a particular Cster. It is also demonstrated that the GIAO-MP2 results ar Sperior to tose obtained at the GA0-SCF level. In some cases, the three dmensional arorriaticit ws evaluated in terms of the NCS (nuclear independent chemical shift) vlues. Wheliever comparison wth the 'soelectrolobal carborancs 'ud-ed by vrious Respect is outlined. Supported by the Ministry of Fducation of the Czech epublic (pr 'ect LNOOA028).
1. T. Jelinek, B. Stibr, J. Holub. M. Bakardj lev, D. Hnyk, D. L Ormsby, C. !N. KI ner M.
Thorriton-Pett, H.-J. Schanz. B. Wrackmever and J. D. Kennedy. Chem COMU11111?.. ' 00 1. 1756-1757. 2. B. Stibr, 0. L. Tok. W. Millus. NI. Bakardilev. J. Holub, D. Hn, k and B. Wack-meyer, Angew. Chem. Intl. Ed. Engl., in pess. 3. J. Holub, T. Jelinek, D. Hnyk, Z. Pzak, 1. Csarova, M. Bakardjlcv and B. Stibr, Clicni. Eur J 2001 7 1546-1554. 4. T. Jellnek, D. Hnyk, J. Hlub and Stibr, not-a. hein 20 4, 45 2-4513. 5. A few upublished examples will be sown.
97 P-20 RU0410078
PIIOSPHACARBABORANE 01EINUSTRY THE REACTION Fnitlo-7,8,1 I-PCIB8111,
AND ITS 9-CI DERIVATIVE NVITH 5-C Hi-Fe(CO)212
Josef Holub', Mario Bakardji, eVa , Boliumil tibr a and vana CisafOVdb
Ji isl itute qf In organ ic C17ennswy, A cadenii of Scien ces of th e Czech Republic,
250 68 -- nar Pi-ague. the C:ech Rpublic, Research CenireforNe v Inorganic
Compounds and.4tivanced Materials, University Pardubice, e-niaik holuboa iic.cas. cz
CharIcs Ulihcrsity, Facultv ofNatw-al Sciences. Hlavova 2030, 128 4 Pi-ague 2,
the Czech Republic. e-inaik cisai-ova(anatur.cuni.cz
The reaction between [i7ido-6,9-CBsH,(f_ anion dsodium salt) [1] and PC13 in
dichloromethane resulted in the isolation of the eleven-vertex nido phosphadl'.arbaborane
7,8,l1-PC,%H,1 2 and its 9-Cl erivative. Complexation of nido-7,8,ll-PCB81J,, via
5_C reaction with [if'-CiH -Fe(CO)212 in xylene at reflux or 24 h ave [1-(q H+closo-1,2,3-
FeC-BsH,(,] via P-vertex removal.
,A similar reaction between 9-Cl-nido-7,8,1 -PCBJi1(, and [il -Cz;H -Fe(CO)211 in boiling
xylene for 24 11 gave two main products dntified as [3-C]-I-(q' -C5Hi)-closo-1,10,2,4-
FePCBs1JJ and [7-C]-]-(,q -C ;H )-closo-1,10,2,4-FCPCBgHg]. The structures of these
compounds were determined by an X-ray dffractio aalysis. ndividUal compounds were
characterized by mass spectrometry and multinuclear I IB, 1 H and 31 p Stroscopy
combined with two-dimensional [''B-''B]-COSY NMR measurements.
This work was supported by the Ministry of Education of Czech Republic (project no.
LN,10OA028). We also tank Drs. J. Fusek and Z. Pzdk for NMR measurements and ass
spectra.
1. tibr B., Pe§ek J., Heh-ndnek S.: Collect. Czech. Chem. Commun. 38, 335 973).
2. lolubJ.,OrmsbyD.L.,KennedyJ.D.,GreatrexR., tibrB.:Inor-.Chem.Coi-nmun.3,
178 2000).
98 P-21 RU0410079 MAGNETOCHEMICAL INVESTIGATION OF THE SALTS OF NI"(11,10 - C,,H,,N,),12+ CATIONS WITH ANIONIC DERIVATIVES OF ORT110 - CARBORANE 12), M = Mn; Cu; Ni
V.N. lkorskii, M.K. Drozdova, V.V. Volkov
Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberia Banch, Novosibirsk 630090, Russia,jax. 7(3832) 34 - 44 - 89.
'12 Caton, A magnetochernical investigation of the salts of [Ml' (phen - 11 s containing paramagnetic atoms Mn(II) d' Cu(II) d9, and diamagnetic Ni(11) is performed. Anionic components of these salts are: [R)C21-1121 , [HCb ; [Co ... B,)CHII)2 , CoCb,]-; I d' is paramagn [Ni"'(139C21-11021 1NiCb2j N1 edc. The neutral complex [Mnl,(phen)2(SCN)21 0 is also investigated. The salts of the row under consideration contairl paramagnetic centres of different types, as well as planar (phen) fragments and three- dimensional aromatic structural fragments HCb]-; MCb2l-. Interactions are possible that affect their agnetic properties. Magnetic susceptibilities (,-/) were measured with SQUID magnetometer. Results are shown as plots of temperature dependencies of ( y 1) and fijy(7 , Fig. 12. The 7-) dependencies at T >20 K are described by the Curie - Weiss aw: X= CI(T-0). The C, 0 parameters and exchange interaction energies zJ are calculated. Complex C, cm 3 K/ mole 0 K zJ cm [Mn (phen)2 (SCN)d 4.30 - 041 0.06 - 0.05 [Mn (phen)3] HCbJ2 4.29 0.26 0.09 0.03 [Mn (phen)3] CoCb,12 4.32 0.43 0.15 0.08
At T ;z,2 - 30 K differences are observed in the behaviour of'Li it (T) Plots Crves or te [Mn (phen)31 HCb]2 and [Mn (phen);] [Co Cb,]2 salts exhibit maxima at about 20 K. ThIS fact is the evidence of additional ferromaunctic weak interactions. Other slts of the series under consideration do not exhibit this -effect A consequence of the ferronlaunctic xchange interactions is also positive --J values. For the Mn(II) atoms iii,, = .% B-14. 203 K. Surroundin- 1Yands do not affect this value. Low-temperature effect of fe-romagnetic interactions is a novel fact in the chemistry of borane derivatives.
X-',mole/an' 4ff.M B. Uof.m B 6 5 60 0 5.9 [Mr,;hen,)l[NiCb 2
5.8 5.5 40 5 0 [Mn(phen).(SCN).l 5.7
5.6 [Mn(phen) l-'[HCbl, jNiPhen,)j[NiCbl'
C) [M11(phen),l, '[CoCbj2l 55 35 (CuPhen,)j[NiCbj1
0 0 50 1 0 1 50 200 250 30( 0 50 100 1110 200 250 300 T K TX Fig. I Fig.2.
This work was supported by the Rssian Fundation for Basic Research-, Grant 0 1 03-32428.
99 P-22 RU0410080 SYNTHESIS AND CHARAcrERIZATIONS OF NEW I VERTEXai-achno- THIADICARBABORANE ANION 17,8,11-SC21381-1111-
Zbyri& Janou§ek, Josef Holub
Institute oflnoranic Chemisti-i%Acadenn, of Sciences of th Cech Republic, 250 68Re-," ear Prague, Czech Republic, Resem-ch Centei-fibi-New Inoi-ganic Compounds and,4dvanced Alatei-ials, Univei-siti, of Pai-dubice. e-mail:janousekCqjic.cas.cz
An area of continuing importance in polyhedral boron chemistry is te development of new ici -,, iith-t'c method bv wh'ch atorn insertion eactions leading to expanded cage or fivbride cluster can be accomplished. Traditional sulfur-insertion reactions leading to the fori-nation of thla- or dirl-ilaborane clusters had included the reaction of boranes or carboranes
With SLIKer rea(Tents sch as ami-nonjuni polysulfide 1,2], thionitrosodirnethylarnine 1,2 or KHSO, [3]. However. several yars ao te reaction of arachno-4-CB81414 with emental sulflir in the presence of triethylainine leading to sulfur atom insertion was dscovered 4].
Similar eaction f sulfure wth nido-6-SB,)l1j(,- anion results in sulfur insertion into te ndo-
SB,, caule franic \ork to produce the ew arachno-dithlaborane CUStCl- anion, arachno-2,3-
S 13,,1-11( - [5] I or contribution w report a simple sulfur-insert reaction into 17ido-6,9- C,B, Hjo- in T1F tat as allowed the production of a new thlodicarbaborane anion SCB0111-01)which sonlyasecondrepresentativeof 11-vertext-ii-achl7O-CILIsterseries:
6,9-CB8H,( 2- + S ------> SC2B8Ho 2- 1110 -> SCBsHj,-
Physic-chemical and structural properties will be discussed.
Support from the Ministry of Education of the Czech Republic Pr 'ects NOOA028 is
Z71greatly appreciated.
1 Rdolph R. W., Pretzer W. R.; hm-g. Synth. 22, 226 1983)
2. liertler W. R., Klandberg F., Muetterties E. L.; Inorg. Chem 6 1698 1967)
3. Ple, ,ck J., eh-n nek S., Janoukk Z.; Collect. Cem. Commun. 42, 785 1977)
4. 11flU J Jelinek T., Plekk J.. tibr B.. fidi-ridnek S.. Kennedy J. D., J. Chem. Soc.. Chem.
Commun. 389 ( 1 99
I 1()Iuh J Wille A. E.. tlbr B.. Carroll P. J., Sneddon L. G.- 1nor,,. Chem. 3 4920, 1994)
I W P-2 3 111111i 'l,1[ IR 1I IPIII[ 111IIII,III RU0410081
SYNTHESIS OF NOVEL BORON CONTAINING UNNATURAL AMINOkCIDS AS POTENTIAL BNCT AGENTS C I aj igorge W. Kabalka -Liang Yao, James F. Green, and Nisha Natar 'an, Bhaskar C. Das Mn Zhongzh Wu
Department of Chemisity, The University qj'Tennessee Knoxville, TN 39996-1600 USA, etail kabalka wk.edu in the last decade, there has been considerable interest in boron neutron capture therapy (BNCT) a binary approach to the treatment of cancer in which a substance containing boron- 10 is selectively delivered to tumor tsue por to irradiation by neutrons. The clinical success of BNCT depends on two factors: effective delivery of a sufficient qantity of boron to the targeted tumor and a neutron flUX sufficient to achieve the prerequisit nclear reaction while minimizing damage to healthy tissue. Early BNCT clinical trials were dsappointing in that they failed to achieve either of these goals. However, sonificant advances in te modification of nlear reactors and the design of tumor seeking boron-containinLi phan-naceuticals have been made in recent years.
Nuclear medicine studies at the University of Tennessee PET center have revealed that unnatural, cyclic amino acids Sch as carbon- I labeled -aminocyclobLitanecarboxylic acid selectively localize in tUrriors Sch as alloblastorna MUltiforme (a bratn tLimor) and malignant metastatic melanorna. For tis reason, we have focused Our efforts on preparing cycliIC Cimino acids containing boron. Compounds I and 2 ae representative of a series of re,-Igents containingZD a single boron atom. In addition, e have prepared a series of cyclic aino acids
H2N CO H H2N COH
OH OH B B OH OH 2 containing mer-a-carborane moieties which have been made more water soluble by attachment to carbohydrates and polyol pendant grOLIPS 1,2,3)]. The syntheses of representative examples will be discussed.
1. Srivastava, R. R.; Sin-haus, R.; Kabalka, G. W. J Ora. Chem., 1999. 64, 8495. 2. Das, B.C.; Kabalka, G. W.; Srivastava, R. R.; Bao, W.; Das, S. J. Organoinct.Chem. 2000, 614-61-5, 255. 3. Kabalka. G. W.; Das, B.C.; Das, S.; Li, G.; Bao, W. Sitilett 201, 1419.
lot P-24 RU0410082
130RONIC ESTERS AS PRECURSORS IN RADIO10DINATIONREACTIONS
Gcorpe W. Kabalka Murthy R. Akula ad Zjanhua Zhang
Delwi-tmem qf Clicinisti-i-, Te Univci-siti o Tennessee Knoxiille, TA.)'9996-1600 USA, e-mail: kaba1A-a utA-.edu
The se of ort.,,arioboranes as Himmediates for radjohalogeriated phamiaceuticals has been of interest i our laboratory for oN er twenty ears. We developed te use of boronic acids and inalkylbor.mes as precursors io radlohalogenated compounds 12]. owever the reaction
,:011ditiOnS FOqUired to prepare the boron precursors were often not suitable for containin- reactive substituents such as esters and ketones.
C 011SCJLICI`Iljall . boron precursors are not routinely used in radlochemistry. Recent advances M p.i)) idlum-catalyzed conversions of haloarenes to arylboronic acids prompted us to reexaminc the halodeboronation as a vable approach for radiolodination. r lbot onates I and Z)-vinylboronates 2 were prepared from te respective iodo compounds
ViU SLI/Liki C0L1j)11'nL 3 and N crc conveniently converted to the corresponding iodine-123
labeled arvi iodides 3 ied (Z)-%?invl iodides 4 usim, Nal 23 ad chlorarnine-T. Te functional group tolerance nd wide applicability of this methodology series to make ts aproach Suitable or te preparation of a wide variety of radlopharmaccuticals.
0 Na 1231 B V.- 11123i 0 Chloramine-T R ___ 3
H H Na 1231 H H
R B 0 Chloramine-T R 1231 0
7
2 4
1. Kahalka, G. W., Gooch, E. E. and Otto,, C. J Radioanal. Chem. 1981, 65, 116. '. Kahalka, G. W'.,- Varma, R. S. Teirahedron 1989, 45, 6601. 3. smarna. T.. Murata, M. and Miyaura, N. J. i-g. Chem. 1995, 60, 7508.
I 2 P-25 RU0410083
ORGANOBORANE C"EMISTRY IN NON-TRADITIONAL SOLVENTS
George W. Kabalka, Venkata'ah Bollu, Vasu Narnboodiri, Wclllan,, Bao, and Li. Wng
Department of Chemistrv, The University oj'Tcnncssee Knoxville, TN 39996-1600 USA, e-mail: kabalka( vutk edit
In recent years, chemists have developed new synthetic methodologies tat are environmentally benign. Not surprisingly, ionic liquids and water have been found to be useful in a number of these methods. Ionic liquids have attracted interest as raction media synthetic manipulations because they exhibit a lack of vapor pressure, ease of reuse, absence of flammability, and a tolerance for large temperature variations [1]. As a example, we recently reported that simple trialkylboranes can be utilized to reduce carbonyl compounds at relatively odest temperatures 2]. We have found that ionic lquids such as 1-butyl-'-niethvliiiildazolluin tetraflUoroborate and the corresponding ethyl derivative are excellent solvents for allylboration reactions. Te reaction yields are good and the products are readily isolated. 0 of]
H + B(OR)2 HO
In addition, we have found that alcohols and water can b tilized s solvents to carrv Ot metal catal zed carbon-carbon bond formin- reactions nvoh,'M2 boronic acids [31.
Pd + B(OH)2 CH;OH
1. Pagni, R. M..- Kabalka, G. W., Lee, C.; Malladi, R. R.; Collins. B..- Conley, N. In Rogers. R. and Seddon, K. American Chemical Sciety Smposium Series, in press. 2. Kabalka, G. W.; Malladi, R. R. Chemical Communications, 1-000, 2 19 .
3. Kabalka, G. W.; Namboodiri, V.; Wang, L. J Chem. Soc., Chein. Com1n., 2001, 775.
103 P-26 RU0410084 NOVEL CARBORANE DERMXT IVES
AS NUCLEAR VITAMIN D3 RECEPTOR AGONISTS
Hiroyuki Kagechika,' Kyoko Yaguchl,' Tornohiro Yoshimi,' Erniko Kawachl,' and Yasuvuki Endob
'Graduate School ofPhartnaceuticalSciences, Te University of Tok),o,
Ron-0.1 1 Bunkvo-ku,- Tok-vo- 113-0033, Japan, e-inail: kageCa inolf u-tokyo.acjp Tohoku Pharniaccutical Universin' 44-1. KoinatsushlinaAoba-ku,Sendai 981-8558, Japan e-niaii: vendwa ioho1%-u-phartn.acjp
Applications of te unique structural and chemical properties offered by icosahedral carboranes (dicarba-closo-dodecaboranes) have much attention in te field of biomedical sciences. PreviousIv \e reported that carborane is potent hydrophobic pharnlacophore in the structures of nuclear receptor ligands such as retinolds and estrogens In this study, e found tat several
carborane derivatives are potent agonists of nuclear vtamin D- receptor (VDR). Vtarnin D3 plays significant role in cell differentiation and proliferation as ell as in calclurn-phosphorus homeostasis Te development of novel synthetic analogs have attracted mch attention in the Field of dermatology ad oncology.
Considerim, the stricture of Ioc,25-d1hydroxyvitarnin D3 (1,25-VD3), Xve designed the para-carborane derivatives having two substituents o te carbon atorns (the generic structure 1), vhere the carborane rnoiety corresponds to the CD ring of the 1,25-VD . The b1oloulcal activity of the synthesized compounds was first examined in terms of the ability to induce differentiation of human promyelocytic leukemia cells HL-60. Among them, compound
2 is the most potent inducer of differentiation, and EO value is I X 07 M, which is one-sixth of tat of 1,25-VD3 (EC5( value 1.8 x 10 M). The competitive binding assay showed that
compound 2 is a potent ligand of VDR. Since oly a few vitamin D3 derivatives without CD ring have been reported, the potent vitamin 133-like activity of carborane derivatives with ique structure 'de further for employing vitamin D in un I and chemical properties may provi clinical use.
X *Ri H RIM O" COH
H(3' H 110" OH HO--- OH
1(j,.25-1)1hvdroxyv1tam1n D3 2
104 P-27 11111 I 111 11 1 111IN 111 1 1 I U410085
SYNTHESES,,VND STRUCTURES OF PANO-STOOL TYPENIANGANESE COMITEXES
OF BORANE-LEWIS BASE ADDUCTS
Taeko KakizawaYasuro Kawano, Mamoru ShIrnot
Department of Basic Science, Gi-aditate School of A rts and Sciences, Universitl-qj'To-vo, Koinaba,
Megiwo-ku, Tokyo, 153-8902, Japan, e-mail: c,.Yhinioi((L',iiiciil.ccc.ii-toki o. ic-.jp
Much ttention has been focused on cy-complexes because of their key role in chenilc"d ractions of(7 bonds. We report herein a new G- complexes of borane-Lewis base addUCtS BFI,-L.
Photolysis of piano-stool type manganese complex [CpMn(CO).-] in the presence of 13113-L (L I -L) I a L = N M . I b PM c,,), NMe3, PMC3) afforded borane G-complexes [CpMn(CO)2(11 -1311; III which te borane lgand bund to the manganese atom through a B-H-M thrcc-center mo-electron bond [I].
S VH H SL2VI h , I 0CW ,Mn + BH3-L 0C Mn .B 0C co oc H L (la 1L = NMe3- lb. L PMe3) X-ray crystallography revealed tat the coordination mode of te borane hgand %%;-,i,, end-on. Pic I - bonding between borane Hpnd and metal i I can be aCCOUnted y tfc strong c--,, onatlon 1om ili,
BH a bond to etal. Te r back-donation no the BH G' orbital is \,lolecular orbitii, w'II be also discussed.
H /B
H N 7 P
la 1b 1. T. Kaklziawa, Y. Kawano ad M. Shirnoi, Organometallics, 2001, 2, 32 1.
105 P-28 RU0410086 3-ALLYL-3-BORABICYCLO13.3 I INONANES
A.L.Kirionova a, A.V.Gelderikh". S.Yu.Erdyakov', M.E.GLIrskli", Yu.N.Bubnov'b
N. D. Zelinsky Invinae of Organic Chemistt-i' Rssian Acadenn, of Sciences, 119991, GSP-1, Leninski-In-osp. 4, Moscow, Russi, e-mail boi-Cacacnioc.ac.ru-
4..V NcsMcl -anov Institiac Ort, ' noelcment Compounds, RussianAcademi, ofSciences, 119991. avilova sti-., 24. Moscow, Russia.
-)-A],IN"I-' -borab'cNelo[').-').Ilnonane. - I ad 2 were obtained through transmetallation reaction or OU an exc .hange reaction with triallylborane.
B N _ Fir B
EI'O. 32C'C R 14 la). lb). Ph ) W-OIe. P 11 68-80%
Me OMe
Me B-( me Bl ' Me 131 Me 011 Me I In meoli e AIIB Me- 11 - , v. EtO 2WC
Me Me 2 Me
No [1,3TsIgmatropic boron shlift (pci-marient ally] rearrangement) is observed i te obtained compounds at room temperature (1H NIMR frequency 200.1 3) MHz and 13C frequmcy 50.32 MHz). 0 OH 3:4 Ib79:21 Me Me + Ic 76:24 HIN OH AI 13 93:7 3 4 7u-Substituted 3-allvi-3-borabicyclo[3.3.1]nonanes react with 2-methylcyclobexanone to
(T-ve te prodUCtS of equatorial attack on the carbonyl group predominantly. This %vork was supported by Russian Foundation for Basic Research (Grants 01-03- ')2465. 00-15-97378 and 02-03-32248).
106 P-29 RU0410087
ISOSTERIC POLAR REPLACEMENT OF A C-C FRAGMENT WITH B-N: SYNTHESIS AND PROPERTIES OF NE"A'POLAR LIQUID CRYSTALS
Serhii Pakhomov," Plotr Kaszynski, Yri N. Bubnov, bMikhail E. GUrskil,
and Victor G. Young Jr.c
a Organic MaterialsResearch Group, Department of Chemistry, Vanderbilt Universit-i-,
Nashville, TN 3 7235' b nstitule of Organic Chemistry Rssian Acadeiny of Sciences,
Moscow, Russia 11 7913; c X-ray CrjsiallographicLaboratory, Departnient of Cheniistrvl University of Minnesota, Twin Cities, M 55455
Substitution of nitrogen and boron for the two carbon atoms in ethane gives a polar isosteric amine-borane complex wt a dipole moment of about D. Similar substitutions in carboranes sch as la, and bicyclo[2.2.2joctanes, such as 2a exhibiting liquid crystalline properties, leads to polar analogs with longitudinal dipole oments. Such polar materials re desired for a number of nematic liquid crystal display applications. Aside from pract lical applications, tis isosteric polar substitution offers a unique opportunity to studv te effect of polarity on mesogenic properties. For instance, replacement of two carbon atoms in a nerimtic carborane drivative la results in a dramatic stabilization of crystalline phases i te polar 14 D) analog I b.
C5H, I- 7H15
C5Hjj -&1402 --OCH3
I a: X=Y=C b: X= B, Y =N 2 a: X=Y=C b: X=BY=N While the chemistry of boron clusters is well advanced. the snthesis of borabicyclo[2.22]octane ring is still in progress. In parallel, we evaluate the thermodynamic stability and dipole moments of complexes such as 2b using quantum-mechanical calculations W also conduct experimental and theoretical studies of 1-boraadamatitane. a close analog of I borabicyclo[2.2.1loctane, and its complexes 3 ad 4 with an emphasis on their olecular structures, polarity, and chemical and thermodynamic stabilities.
-B 3 4
107 P-30 RU0410088 TIIE EFFECT OF CLOSO-BORANES ON LIQUID CRYSTALLINE PROPERTIES
oerlillC Pakhomov, Andrew G. Dou-lass. Wktor Pecek, James E. Harvey, Andrzc' Balinski, Krystyna K. Kulikiewicz, and Piotr Kas zynski*
Oi-u(mic-MaterialsResearch Gi-oul), Departnientof Chemistry, 1anderbilt University, Nashville. TN 37235: http:llii-iiii,.iaiidei-bilt.eilulAiiSICliet77isti-y101111-g
U 11usual steric and electronic properties of boron closo clusters provide opportunities for preparation of new materials for applications in electrooptics and fr study of fundamental aspects imparting liquid crystalline behavior [ 11 The molecular syrninetry of the clusters and conforinationa poperties of their de-]%ati'Ves permit to stuck teric and conforniational effects oi te incsophase stabilit 2 Te forinal substitution of nitrogen and boron for the two carbon atoms M non-polar carborane derivatives aives polar sosteric analogs ad allows the study oftlic effect of polarity oil ineso-enic properties. For instance, double polar replacement M la significantIN increases the longitudinal quadl-LIDOle moment, in lb, wich coincides wth increase of the TN-1 transition temperature bv 120 OC. Also te study of close stnictural analo(-,s of o-, ni-. and p-carborane give important information about te role of magnitticle and orientation of molecular dipole oment n stabilization of a mesophase.
1 a.X=Y=C.bX=BY=N
C,H,50 5H, 2
The lar-c electronic polarizability and cylindrical shape of the clusters results in a high isotropic refractive index and o brefringence of their mesogenic erivatives 3 The electronic sructure of these largely UV transparent clusters allows for either minimal (12- vertcx clusters) or extensive (10-vertex clusters) electronic interactions with pi substiftients [4] Te former nables engineering polar materials with marginal UV absorption, while some derivatives of the latter exhibit large charge transfer absorption bands and are suitable for rnesogenic NLO chroinophores such as 2.
1. Kaszvnsk1, P., D01.1-lass, A.G. J. Oi-anonicial.Chem.1999, 581 2. 2. Ka. ,zynski. P., Pakhornov. S.; Tesh, K. F., 'oung, V. G. Jr. h7org. Cl eln. 2001, 40, 6622.
JaSS A G.. Czuprynski, K., Merzwa, M., Kaszynsk', P..J. Mawr. Chenz., 1998, 8,
4- 1'akhomov. S.,- Kaszynski, P.-, 'oung, V. . Jr. Inor-. Che/11. 2000, .3 , 2243.
IN P-31 III I 1 I[ # 111[ 11 11 1 I[ RU0410089
APPLICATION OF THE ELECTRON LOCALIZATION FUNCTION ELF TO PERCIILORINA] ED CLOSO-FIETEROBORANE CLUSTERS
Willi Keller', Wolfgang flaubold', Andreas Savin I, and Patriclo Fuentealba 3
Institutfir Chenfie, niversitdt Hohenheim, D- 70599 Stuttgart, e-mail: kellervv tini-hohenheim.de
2Laboratoirede Chimie Th oriqtie, CATS et Universit Paris VI, - 75252 Par.7s CEDEX 0.5
3 Departamento de Fisica, Universidadde Chile, Santiago
The Electron Localization Function (ELF) has been proved to give appreciable insight into the bonding of molecules, clusters, and solids, not only for covalent compounds, but also for intermetallic systems [1]. ft is suitable also for systems ith high symmetry and multicenter bonding. The ELF has values close to unity in regions of covalent bonds, lone pairs or core shells, and is close to zero in regions between shells. A color code based on a map is used to indicate hgh or low values thus dstinguishing between molecular regions with hh or low electron density. Previously, by this means the electronic structure of several polyhedral boranes. as .g. BR,_"1
BloH14, B404, BBrq or the danion BBr92- have been investigated 21. SUrprisingly. polyhedral heteroboranes have not been subjected to.ELF calculations so far, which promised LIS to bringy insight into the disturbance of the ideal electronic custer pattern nduced by the Introductio of heteroatorns. Our first attempts in this field focussed on the ELF calculations of the octahedral diphosphahexaborane cIoso-l,2-PB4Cl_4 [] and the 1cosahedral closo-SB, C!, 4 The ELF isosurfaces of these csters in addition to BHi( 2- B12F11, 2 and BHg which N nc!Llded for the purpose of comparison, are shown and discussed.
1. Savin, A.; Nesper, R.; Wenaert, S.; Fissler, Th.Anaeit,. Cheni., Int. Ed. Eli-I. 1997, 36, 1808. 2. 1-16tile, W.; Grin, Y.; Brkhardt, A.; Wed;.,(,, U.; Schultheiss, M.; von Schnering, ti. G., Kellner, R.; Binder, H. Journal of Solid State Cheni. 1997, 133, 59.
3. Haubold, W.: Keller, W.; Sawitzki, G. 4n('CIV. Chem., Int E. Enal. 1988, -17, 925. 4. Einholz, W.: Sch5fer. R.; Keller, W.; Vogler, B. Z. Natwfi)rsch. 1997,52 b, 221
109 P-32 RU0410090
L-BORON-PHENYLALANINE IN NcrOF SPONTANEOUS MELANOMA IN DOGS
V.F.Khokhlov, I V.N.Koulakov 1, I.N.She'riol, VA'.Meshchcr1kova2, A.A.Wainson 2 V.N.Mitln2, N.G.Kozlovskaya", K.N.Zaltsev', A.A.Portno V3
State Scientilic Centci - Instititle of Blophi7sics (SSC-IBP), 123182 Afoscow, Zhil-opisnall( il., 46; Blokl7ill Cancei-Rescai-ch Centei- ofthe Riissian.4cadcm.v oflfedical ScienccS (RCRC RAHS), 11-5478Afo, coii,,K(islii7-skoieSl7osse,24,-3 AfoscoiiFnaincei-ing Phl'SiCS 112SM111C (SMIC univci-si .tv), 115409,11oscow, Kashii-skovc shosse 31
Durim4 te recent vears- an experimental base for the neutron capture therapy (NCT) has been created on te base of' te nuclear reactor IRT MEPhl [II. Preclinical studies of the NCT nodality used "'13-boron-L-pherivialanine as te drug form of borate ether with D-fructose (BPA-F). Te chernicai pui-ItN of te parent drug o' Io13-boron-L-phenylalanine produced by Katchern Czechia) was Q8 O ad I B nucild's concentration rate - 99.7 . All dous passed a cniplete. clinical exa,1,111=1011. IIICILidilh! the peripheral blood analysis. Immediately prior to the irradiation, te dogs undervent special prernedication. The dogs with SpOillarICOLIS inclariorria had BPA-F 200 malki-0 administered intravenously 2 hours prior to the irradiation. Te irradiation tirne aried fr m 1.5 to 2 ours depending on te tmor size and site. The turnor siles and te results are shown in te table below. Neutron capture therapy n dous wth spontaneOLIS melanoma
JV2 Tumor site, size Turnor deposit. size Turnor state after irradiation I Mouth, (3x3x4) cm 3 lymph node, 3x')x 1) involution of cm3 turnor Exterior of labruin, (3x3x4 cm no involution of tumor 3 Interior of labrurn, (3x2x 1) cm 3 no involution of tumor 4 Interior oflabri.1111, (3x3x2) cm 3 lymph node*, (3x2x 1) involution of cm tumor 5 Foreleg 2 nodules I st - (2x3x I cm 3, I rnph node*, 3 x I XI) involutio Of and 1-nd (2x2x 1 cm 3 cm3 tumor *Sur,,Ically removed before the NCT irradiation Detectors for the registration of poton and neutron dose were located on the immobilized dog's body Srface. Also, a biological dosimeter developed by us was used 2]. Along the tme of irradiation, certain depth of narcosis and initial level of rnicrocirculatioll were remotely maintained. During the irradiation, the animals were under observation via a vi'deo camera. The states of the respiratory system and cardiovascular system were controlled, and records of the rspiration rate, heart rate, and arterial blood pressure were made 3]. The data obtained prove high effectiveness of te NCT in treating melanorna, with complete recovery after one irradiation session for the cases of treatment on early stages of illness. The work has been performed wth the support of te RFTD (R-F Ministry of Science) and ISTC (Pr('ect)i 1951).
1. V.F.Khoklilov. el al.. Frontiers in Neutron Capture, ed. by Hawthorne et al. Kluwer Acadc1111C/PlC11L1111 PLiblishers. N-Y, 2001. p.425-432. v.F.Khokhiox. c W EnL,'ncer n- Phvs1cs. 2000. N d, 52-55. K.N.Zaitscv, el a., Atomic Energy, v.91. issue. 4 20 I, p. 307-314. P-33 RU0410091
COBALT COMPLEXES WITH MONOANIONIC CARBORANE LGANDS jq-L-7,8-C2B-)Hj(jj (L=SMei, NNIe3, Pv)
Peter S. Kitaev, Vladimir 1. Meshcheryakov, Gennad I V. Gr1ntse1c%--Knyazev, Pavel V. Petrovskii, Alexander R Kudinov'
Nesmeyanov Institute of Ot-ganoelement CompounA Russian Acadeni'v oj'Sciences, 119991 Moscow, Russia, e-mail: arkudinovCq,ineoY.ac.r1t
Cobalt complexes with dianionic dicarbollide ligand [7,8-CBH i j2- are well known I Analogous complexes 25, containing monoanionic substituted dicarbollide 11(yands [9-L--17,8- :_ t C2B9Hlo]- (la-c) (L=SMe,, NW3, PY) , were prepared in this work.
L Co Co L L + Co (MeC
2a-c 3a-c L
[CP I 1 a-c ICP COC112
Co Co L L
a: L=SMe2 b: L=NMe3 4a-c c: L=Py 5a-c
Complexes 2 and 5, which are analogous to cobaltocene, are easily oxidized to the corresponding cations 2 and 5. Structures of 2aBF, (two diastercomers) and 3.c were determined by X-Ray diffraction.
1. I.B. Sivaev, V.I. Bre-adze, Collect. Czech. Chem. ommun., 1999, 64, 783. P-34 RU0410092 TIlE FIRST EXAMPLE OF ORGANOBORArION OF A TR10SN11UNI CLUSTER
0. A. Kizas, E. V. Vorontsov, F. M DoIgushin, Yu. N. Bubnov
A. A'. Nesinevanol, Invitute of Oi-anoelement Compoun(Is Rssian Academy of Science, Vavilova 2, 119991, Moscow, Russia
Products of hlo ad ivdroboration of etal complexes are known to be itermediates of .some catalytic processes. However tere I's I ttle data [I on transformations of or-anoboranes on carbon\,] c.)rnplexes. We fund tat H-0si(CM, reacts wth triallvlborane uder mild conditions to yield
CILIStCr 1 (87%) which as been caracterized by H, and 1113 NMR spectra and its
s1rL1CtU1'C has been continued by X-rav analysis. The reaction s accompanied by isornerization of to allv] fragments at te boron atom into (E)-2-propenyl groups -- coordinated to two
0SMIL1111 at011IS LInd b reduction of the third oe into te propyl group.
C(19)
(CO)4 Os 17) C(5) C(8) C'2 (OC)30S OS(CO)3 I0, 4 C(61
H H 2) HC H K CH3 010)
CH2 C(3 CH3 C(131 CM C 71 CH2' 01)
III tile I 13 NMR spectrum the signal of I for the boron atom is in high field =4.55 ppm) typical of four-coordinated boron derivatives. However, X-ray date evidence for the planar structure ofthe organoboron fragi-ncnt in I and there is no nteraction between the boron atom
and CO groups f the 0SMILIM triangle. Thus. cluster I contains d](2-propenyl)-propylborane air- and oisture stable and can b readily solated by as a 11,and. ('ornplex I I I I I I chroinatooraphy on silica-gel.
1. L. karton nd 1). K. Srivastava, i CMC41, vol. 1, p. 275. 112 P-35 IIII] [] 111]11 1 1[ 111 RU0410093
COMPLE-rE "B SPECTRALASSIGNMENT OF 3-AMINO-1-METHYt,-1,2-DICAIZBA-cli).iio-DOI)EC kBoI'%,kNF Kodess M.L, Ezhikova M.A., Levit G.L.. Kra-snov V.P., Olshe ,skaya V.A., Kahnin V.N.. Charushin V.N., Chupakh1n .N.
Institute of Organic Synthesis of'RAS (Ural Div), Ekaterinburg, Russia, e-mail: ca(aJos. il-an. rt.
A.N. NestneyanovInslitute of 01-anoelementIt, Compounds qf'RAS, 28 Vavilova St., 119991,11mcow, Russian Federation,e-mail: vkulin(,vineos.ac.ru
The complete assignment of B signals in NMR 11 B spectrum of 3-amino I methyl- 1,2-dicarba-closo- dodecaborane C(CH3)CHBI(H,)NH2 has been performed. Ten signals of non-equivalent boron atoms with the line wdth ranging from 6 to 0 Hz h% c been observed in the 13 'H,' NMR spectrum in CDCh at 128 MHz fquency. Te low-field sgnal of B 3 has been easily identified due to the absence of the splitting i te protOll-COLIpled SCCtIL1111. In which other signals of boron atoms ge doublets with approximately eual CnSLIntS 165 HZ). CH,
NH,
2 4 C' 0 B
114 1 9
12
Analysis of cross peak patterns observed in 2D proton-decOLipled ''B-''B honlonuclk ,r correlation experiments (COSY. DQF COSY and INADEQUATE) make it pcssible to dvide RI I atoms into tree groups depending on the nmber of ajacent atorns: three and 6 tir 4 5. and I ), and five adiacent B atoms (- I and I ). It follows tat there are iwo possible . ersions or' B assignment in order of field ncreasing Q, 12. S. 6 5. 7 1 1 I ! or 3, 12 9 S. 6 1 1. 5, 10k Additional nformation was obtained from 2D heteronuclear spectrum HMBC. in which correlations ere due to H-1113 long range Coupling. The cross paks between C-'1 poton and 3 and 2 atoms. alone wth relatively weak cross peaks wth and atoms were observed in the spectrum. So, that the net argument In Spport of the first version of B sgnal assigni-ticnt hs been made based on these observations. The work is financially spported by the Russian Fundation for Basic Research Z:1affairs 00-15- 97390 ad 00-03-40139).
113 P-36 RU0410094
VIBRATIONAL SPEcrRA OF COSAHEDRAL MONOCARBORANES: closo-jBilf1j,011 AND -jBjjHjjCNMe31 AND THEIR nido- DERIVATIVES 13j(11112011- AND Bj(jH12CNMe3j
E.G. Kononova, S.S. Bukalov, K.A. Lyssenko, L.A. Leites, V.A. 01'slievskaya,
TV Al'csinevanov Inslitlac of 01-anoclenlent Conipouncls K4S, 18 Ilavilov str., Moscow 119991, Russia, e-iiiail.-bzikleigiiieos.ac.i-u.
The Rarnan ad IR spectra for four inonocarboranes are reported and analysed. Geornetry
optinlizalion as Carried out for [BIIHIICH]- bN DFT (B3LYP'6-' I 'G(dp) method as weli as calcui,-ajons of x lbrailonal frequencies and mode igenvectors. Basing on te effective selection rules. on Rarnan polarization data, and on the results of the calculations, an assignment of ormal modes to the syrninetry species of C, symmetry point group and to lbrational imles is proposed. The rsults are compared with tose for 'soelectronic
1cosahedral dodecaborate anion B12H12 and 1,12-dicirba-clo, t)-dodecaborane C-,B,(Hi2
SlUdicd earlier [I]. SLICUSSIV Sbstitution of boron atoms i te cosaliedFal cage for carbon aton-is leads to n increase in the vBH stretching frequencies. Te frequency of the stretching vCH vibration of' co. o-[BjjlIjjCfI]- is increased nsignificant]\,, corripared to that of p-
Bl,,H,,,CH- bt the difference in te vCH IR ntensity, reflecting bond polarity, is notable. The bivithins, ode of te cosahcdron ce for (/oso-[BjjHjjCH]- as the sarne frequency 760 crn-1 as forp-131(,H J(C2142- In the vbrational spectra of te nido-anions a decrease in the average vl3H frequencies is observed. tpical for nido-structures [] A weak band wth a complicated contour observed in the re,,jon of 200 m-1 could be assigned to the vibrations of e-itra- hydrogens. The Rarrian spectra of te zwitter-lons [BIIHIICNMC3] and [l3j(,l-I12CNMe3] exhibit abnormally Irish values of the frequencies of the CH stretching vibrations in the NMC fraorricrit, 3045 and 3060 crn- , which could be related to a strono influence of the nionocarborane cage Th C111POUnds studied were snthesized according to the known methods 2,31.
1. L.A.1--citcs, hern. Rev. 92, 279 1992). 2. T.Jellnek, I.Drdakovd. S.Ilefrnanek, BStlbr, Coll. Czech. Chem. Cornmun. 49- 155( 1984). 3. W.] I. Knoth, J. Am. Chern. Soc- 89. 1274 1967). 14 P-37
RU0410095 SYNTHESIS AND STRUCTURAL CHARACTERIZATIONOF NEWBINUCLEAR MONOCARBON RTHENACARBORANES BASED ON CB,,,-IIGkND
Trina V. Pisareva, Vitalil E. Konopley, Fedor M. Dolgushin, Pavel V. Petrovski ad Igor T. Chizhevsky
A.N. Nesmeyanov Institute o01-,oowoelement Compounds, 28 Vavilov Sti-eet, 119991 Moscow, Russian Federation,-e-niail: chizborcc ineos.ac.ru
The reaction of (Ph3P)3RuCl,? with [nido-CI3JI131_CS_'_ in solution of benzene-methanol solution in the presence of "proton sponge" has been found to form binuclear complexes closo-[(q6_C6H5PPh2)Rul-c vo-[(Ph3P)C]Ru]-(V-H)2-CBIOH9-,,OMe,,, n=O (1), n=1 2 3 ad closoj(q6 -C6H(,)RLI]-e.-(o-[(Ph3P)2CIRu]-([t-H)3-CBI,)H8-,OMe,,, n= 4 n=2 (5) as its major product. The minor product which has been isolated from the same reaction mture was shown to have the monOnLIClear 20-e structure 2,2-(Ph3P)2-2-H-3,9-(MeO),-2 I RuC % H7 I thus evidencing that te polyhedral contraction reaction of the starting [nido-CBj(H13]_ 1.111der the action of (Ph3P)3RuCl? has also Ocurred. The structures of 24 have been confirmed by a single-crystal X-ray diffraction study. This work was supported by the ussian Foundation for Basic Research (Grant No 00-03-32824).
PPh2 I "Cl R2 Ru- Ru R3 u PPh-, Meo PPh3 Rb-Cl
PPh3 (1) R = R2 H (4) R = H
(2) R = Me, R2 H (5) R = We (3) R = H, R- = Me
1. .V. Pisareva, I.T. Chizhevsky, P.V. Petrovs-ii, V.I. Bre-adze, F.M. Do gL S in, and A.I. Yanovsky, Oi-ganometallics, 1997, 16, 5598.
115 P-38 RU0410096 THE HARNIACOKINETIC STUDIES OF DODECABORATE DERIVATIVES
LABELED WITH 131 1 FOR PLANNING OF BORON NEUTRON CAPTURE THERAPY
Koryakin S.', Yadrovskaya V.', Ulianenko S.', Savina E.', Bratt,-- v V.2
Vedical RudioloaicalResearch C07tei-, Obninsk, Russia, korsel-llic(4 vahoo.com -Staic Scicntific-Research Instititte.1br Chcmiso-y and Technolog , qf Oi-anoelement Compounds, 38 Shosse Entitziastov, I I 123 - ,Ioscow, Russia
In the last vears te method of boron neutron capture therapy (BNCT) of rnalionant tumors
was sccessfully de\ cioped Te combination of BNCT \th neutron teleradiotherapy can be
a perspective approach to its application. Experimental studies both with BNCT and with
combine nutron teleradlotherap ad neutron capture terapy ae perfim-ned in Obninsk.
The object of ts work was to study features of bodistribution of sodium
merc-Ttododecaborate BSII ad rodanododecaborate (BSCN) (perspective native compound
for BNCT) in mce wilh uclanonia B16 Implanted subcutancousk femoral part of te
paw, sing tile rdioisotope techniques. In tis connection we developed nd carried ot '11) [I. 2. Pharrnacokincti 'N'I'thesis of tese compounds labeled wth radioactive odine (1 IC
CUrVeS for tse labeled compounds administered at ndicative aounts, and te
pharmacokinctic curves for unlabeled BSH ad BSCN administered at terapeutic dose, had
identical profiles.
The results of the dynamics study of these labeled compounds in vitro and in vivo
enabled us to evelop a method permitting to follow for dynamics of boron compound
aCCLIMUlation \ith reference to the patient. It is supposed that an indicative amount of *I-BSI-1
or -BSCN wil be injected to an oncological patient sorne days before BNCT, and then
scanning of turnour zone with a garni-na-charnber will be carried out at a given trne interval. It
'II allow, firstly, to find optimal time of BNCT beginning after administration of the
therapeutic dose of compound ad, secondly, to calculate an expected concentration of boron
-it the oment of irradiation.
This observations were carried out with the financial support of RFBR (project Ng 0 1 04-
(6028)
I .Ullanenko S.E., Yadrovskaya V.A., Savina E.P., Brattsev V.A., Cheln.-farm. J. (i-us),
34(2), 30-3 1, 2000)
- )"adrovskava V.A., L'anenko S.E., Sav'na E.P. et al., Chem. lot-m. J. (1-11s),35(8) 67,
(2001 I 1 6 P-39 RU0410097
ALKILAMINE BORANE COMPLEXES AS SINGLE-SOURSE PRECURSORS FOR NANO-SCALE FUNCTIONAL GRADEDIVIATERIALS ON THE BASIS OF CARBONITRIDE BORON
M.L.Kosinova Yu.M.Rumyantsev', N.I.Fainer', E.A.Maksimovskill, K.G.Myakishev*', V.V.Volkov, I I.P.Dolgovesoval, B.M.Ayupov', B.A.Kolesov', M.Terauch ,2 , K.Shlbata 2, F.Satoh 2,M.Tanaka2
IICh SB RAS, 3 Aad. Lavrentjev, Pr., Novosibirsk 630090, Russia
2RISM, Tohoku U17iversitv, Sendai, Japan
In resent years much attention is given to the preparation of the BCN, thin filins bv chemical vapour deposition technique. The commonly used precursors were BC13, CC14, N, and H2, BC13 and acetonitrile or acetylene and ammonia, BH6 5,25 vol % In N2), methane. and ar-on or nitrogen. Molecules of the RN:BH3 type have attracted considerable interest v researchers as B-C-N - forming sngle-source precursor. Particular attention as been given to the study of new ceramic composite - functional gradient aterials. Gradient rnatcrials are composite materials that smoothly realize te transition frorn one material lt OI1C surface to other material at the opposite surface, i.e. thev contain spatial variations in composition and/or microstalCtLire for the specific purpose of controlling variation in trmal, structura Or functional properties. Nanocrystalline materials have become increasingly important both in fundamental and applied research because of teir nteresting properties due to effects of -rain size and the disordered atomic structure of the interfacial re2ions. In or previous work ] we have demonstrated that h-BN. B,C and BCN, :an be deposited on 100) substrates by plasma nhanced chemical vap0l.ir deposition process using trimethylamine borane complex N(CH-)3:B[I-, and its mixture with ammonia. In this paper, we demonstrate the development and characterization of gradient mterials on tile basis of the boron carbonitride with gradient of chemical composition or grain size. The as--own films were characterized by the following methods: ellipsonletry, fR- and Raman spectroscopy, XRD LISIng synchrotro rdiation, SEM. HREN/T. This work was Spported by Rssia Fundation for Bsic Research (J , 00-03-32507,
JVL 00-15-9744S) and rant of 6h contest-examination of scientific pr 'eCtS Of Young scientists of RAS (grant XL 18 1). 1. M.L.Kosinova, E.A.Maximovskii, YLI.M.Ruinyantsev, N.I.Fainer, F.A.Kuznctsov. NIM A, 2001, v. 470(1-2), p. 253-257.
117 P-40 RU0410098 L-BORON-PHENYLALAN1NE UPTAKE IN MELANOMA B-16 CELLS V.N.Koulakov1, V.F.Khokhlov1, V.V.Mesheherikova2, T.P.Klimova3, V.I.Bregadze3 1 State Scientific Center - Institute of Biophysics (SSC-IBP), 123182 Moscow, Zhivopisnava id., 46, e-mail: sheinoSisrcibph.ru ' Blokhin Cancer Research Center of the Russian Academy of Medical Sciences, Moscow, Kashirskoye shosse, 24 ' Nesmeyanov Institute of Organoelement Compounds, Moscow, id. Vavilova, 28, 119991 Among the neutron capture agents, the most well-known are boron compounds, and, in particu- lar. 1('B-boron-L-phenylalanine (BPA) [1]. Melanoma cells fail to discern BPA from L- phenyla- lanine. which is a natural precursor of melanine synthesized by melanoma cells [2]. Owing to the low solubility of BPA. it is common to obtain borate ethers of BPA with organic molecules that have the a-glycoiic fragment, e.g. with D-fructose. for the administration to the organism [3]. When BPA-lructose (BPA-F) is used, it is critical to define the accurate amount of the ad- ministered arug. required for the maximal accumulation of the isotope "'B in the rumor tissue, and also to define time sufficient for the clearance of tissues, adjacent to the tumor, from the neutron capture agent. Generally, these issues are solved empirically [4]. Therefore, it is of cer- tain practical interest to determine the BPA uptake rate in melanoma cells. In the study. BPA produced by Katchem (Czech Republic) was used. The chemical pu- I0 !0 rity of the drug is 98 °0, and B isotope enrichment - 99.7 %. B-L- boronphenylalanine was the parent drug for borate ether with D-fructose. The-cells were grown in a monolayer. The vi- ability of the cells was controlled in terms of their survival and the colony growth rate. The up- take of BPA by B-16 cells was determined by the method of spectrophotometric detection of BPA in the solution after the centrifugal removal of B-16 cells. The maximums of absorption spectra of BPA, BPA-F and BPAHC1 were found to be identical, which significantly simplifies the spectrophotometric measurements. The results are shown in the table. Interaction between BPA-F and suspension of melanoma B-16 cells .No Concentration of BPA-F in Uptake of BPA-F by a B-16 cell in the process of incu- cell suspension, xlO"6 M /ml bation Prior to incu- Post incuba- xlO"9M Number of Uptake rate, Number of bation tion BPA-F mole- BPA-F molecules, xl010/s cules, xlO14 1 4.904 3.029 1.875 11.291566875 15.683 2 2.452 1.471 0.978 5.889681282 8.180 3 1.442 0.875 0.567 3.414569823 4.742 BPA-F penetrates the melanoma B-16 cells at a high rate, and the way of drug admini- stration to the tumor is not a determining factor. Jn order to reach the desired level of drug con- centration in the tumor, BPA can be administered to the organism in various ways. The direct intratumoral administration of the drug to the tumor can be highly effective. This conclusion is in good compliance with well-known clinical data [4]. The work has been performed with the support of the RFTD (RF Ministry of Science) and ISTC (Project 1951).
\.SnydcrH.R., Reedy A.J., Lennarz W.J., J. Am. Chem. Soc, 1958. 80. P: 835-838. 2. Coderre J.A.. Glass J.D., Fairchild R.G., Roy U., Cancer Res., 1987. 47, P. 6277-6383. 3. Nemoto II, Cai./., Iwamoto S.. Yamomoto Y. }.. Med. Chem., 1995.38, P. 1673-1678. 4. IshihashiM. 9U Intern. Symp. on NCT for Cancer October 2-6, 2000, Osaka, Japan, Ab- slracts, IL-2. 18 P-41 RU0410099 ENANTIOMERS OF 3-AMINO-l-METIIYL-l,2-DICARBA-t7*/.w-DODECABORANE
Krasnov V.P.a, Levit G.L.a, Charushin V.N.a, Grishakov A.N.a, Olshevskaya V.A.h, Kalinin V.N.b, Chupakhin O.N.a
a Institute of Organic Synthesis ofRAS (Ural Div.), Ekaterinburg, Russia, e-mail: b [email protected]; A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., II9991 Moscow, Russian Federation, e-mail: [email protected]
Introduction of a substituent in 3-position of 1-substituted 1,2-dicarba-c/o.s-o-dodecaboranes (12) makes the molecule chiral. No literature data concerning optical resolution of chiral carborane derivatives are available. We have earned out the optical resolution of compound 1 by interaction of racemate with S-naproxen acyl chloride (2) followed by resolution of diastereoisomeric amides 3 using column flash chromatography (SiCK, benzene-ethyl acetate) and acid hydrolysis of each diastereoisomer. Optical purity of amides 3a ([a][)20 +36.9° (C 1, benzene)) and 3b ([a]i)20 + 116° (C 1, benzene)) was determined by HPLC (Merck-Hitachi, hexane-propanol-2 80:1. flow rate 1 ml/min; UV detection 230 nm; retention times xyA 6.0 min and in, 10.1 min) and !H NMR-spectroscopy. It was (de) 93.7%.and 98.0%, respectively.
CH3C CH H+ V 3a 3-B10H9NH2
CH3Q CH BH + V 3-B10H9NHX X-CI 3 a, b H+ 3b
OMe o x = CH, Assignment of configuration was performed by X-ray crystallographic analysis of amide 3a. The optical purity of enantiomers la and lb (ee) was 88.7% n 91.5%, respectively, due to the partial racemization that had accompanied acid hydrolysis of amides 3a and 3b.
119 P-42 IIIIIII RU0410100 ENANTIOSELECTIVE REDUCTION OF OXIMES AND IMINES
Marek Krzeminski and Marek Zaidlewicz
Faculty of Chemistry, Nicolaus Copernicus University, 7 Gagarin Street, 87-100 Poland tnkrzem@chem. uni. torun.pl
Chiral amines and hydroxylamines are extensively utilized in synthetic organic chemistry. In contrast to well-established procedures for asymmetric reduction of prochiral ketones, enantioselective reduction of carbon-nitrogen double bond of oximes and derivatives is less developed. In this study the enanctioselective reduction of selected imines. oximes and their O- methyi and O-benzvl ethers was studied. The reduction of O-methyl ethers derived from acetophenone oxime (1). 3-methyl-2-butanone oxime (2) and 3.3-dimethyl-2-butanone oxime (3) with sodium borohydride in the presence of transition metal chlorides (nickel (II), cobalt (II) and titanium (IV)) and (-)-norephedrine gives the corresponding amines. 1-Phenyl- ethylamine was obtained in 62 % ee, but 2 and 3 were reduced with low enantioselectivity. The reduction of O-methyl and (9-benzyl ethers with borane-oxazaborolidine adduct derived from (-)-norephedrine gave the corresponding amines and hydroxylamines with higher enantiomeric excess (82-92 %).
H THF, 0° on HNOR NH2 I + 24 h Ph"" H3B; PrA Ph - Yield ee H 1a R 54 : 46 92 55
1b: R = CH2Ph 77 : 23 88 92
6-Methyl-2,3,4,5-tetrahydropyridine and imines prepared from acyclic ketones and methylamine were reduced with various asymmetric borane reagents. Stoichiometric reactions of imines with borane-oxazaborolidine derived from (-)-norephedrine provided secondary amines of 13-40 % ee. Higher selectivity (50-74 % ee.) was obtained with borane-5-methyl- oxazaborolidine prepared from (5)-diphenylprolinol.
120 P-43 RU0410101
NEW REGULARITIES IN PROPERTIES OF BORANES
S. P. lonov and N, T. Kuznctsov
Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Leninskii pr. 31, II7907 Russia.
In this work, we continue the study of the geometry and energetics of boranes in the framework of quantum- chemical approximations and the structural thermodynamic model ( ST- model ) [1]. The purpose of the work is to formulate the new regularities in which the energy and geometry parameters change with changing the number of electrons in boranes using carboranes as an example. Theoretical analysis and experimental data allow us to formulate the following regularities [2]. l.When the number of electrons increases with respect to the state where all bonding molecular orbitals are occupied with electrons, meta-isomer becomes thermodynamically more stable.
2. The degree of localization of the electron density on the distinguished bonds and atoms increases with the number of electrons:
3.The bonds on which the electron density is localized are rearranged and stabilized.
1. Ionov S. P. , Kuznetsov N. T.. Koord. Khim.. 2000.V.26. N 5 . P.348.
2. Ionov S. P. , Kuznetsov N. T.. Koord. Khim.. 2001 ,V.27. N 9, P.605.
121 P-44 RU0410102
TIN-FREE METHOD OF THE GENERATION OF ALLYLDICHLOROBORANES
N. Yu. Kuznctsov, F. V. Pastukhov and Yu. N. Bubnov
A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences, Vavilov 28, 119991, Moscow, Russia
Allylic dihaloboranes easily carbomctalate acetylenes and certain olefins. The only described route to these highly reactive boron compounds consists in the transmetallation reaction between allylic tin derivatives and BX.; (X = Cl, Br) [1-3]. We have developed a convenient and environmentally friendly method for generation of various allylic dichloroboranes. based on the exchange reaction between the corresponding allyiic triorganoboranes and BCh. R-,= H; R = R2 2BCI3 R2 2 R-|— r\, R2 = Hexane ~ H -30--10°C
BCI3 BPr, Hexane -Pr - CIBPr2 BCI2 -30--10°C Cl Pr 1 2 These reactions proceed via a six-membered transition state to give 1. which is transformed into thermodynamically more stable product 2 through a [1,3]B shift. Allylboration of phenylacetylene with allyklichloroborane leads to the 1,2-addition product 3 which undergoes intramolecular chloroboration giving rise the compound 4. Deboronation of the latter furnishes 2-phenyl-l,3-pentadiene.
Ph. NaOH Ph .BCI, Ph- B MeOH Cl' Cl c, Yield: 72 -75% 3 4 The diene 6 has been similarly obtained from the borane5.
Ph—= AcOH Yield: 68% MeOH // 1. D. A. Singleton, S. C. Waller. Z. Zhang, D. E. Frantz. S.-W. Leung J. Am. Chem. Soc. 1996, UH, 9986. 2. D. F-. Frantz, D. A. Singleton Org. Lett. 1999, /, 485. 3. K.M. Depcvv, S.J. Danishevsky, N. Rosen. L. Sepp-Lorenzino./. Am. Chem. Soc. 1996, 118, 12463. 122 P-45 RU0410103 PREPARATION OF 6J-BENZO-3-BORABICYCLO|3.3.1|NONANE AND ITS 3- AZA-ANALOGLE FROM DIMETHYL 2-ALLYLPIIENYLBORONATE.
N. Yu, Kuznetsov and Yu. N. Bubnov
A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences, Vavilov 28, 119991, Moscow, Russia
Allylboron-acetylene condensation is well known to proceed through three consecutive steps [1]. Two first stages are allylboration of triple and double bonds respectively. On the third stage intramolecular addition of vinyl-boron fragment to a terminal double bond occurs affording the corresponding 3-borabicyclo[3.3.I]non-6-ene derivatives. We have applied a similar approach for the preparation of tricyclic species such as 3. starting from dimethyl 2-allylphenylboronate 1.
OMe -AIIB(OMe)2
91%
i MeOH TsCI.Py 140° C
ii H2O2/OhT ii BnNH2 toluene 8h N I Bn 88% 4 5 86%
The reaction of 1 with triallylborane at 60 C leads to 2, probably via la. The compound 2 is transformed to the tricycle 3 upon heating at 140° C. In this case the r.ryi-boron bond adds to the terminal C=C bond in 2. Oxidation of 3 with alkaline H2O2 gives rise to crystalline diol 4. The c/s-arrangement of hydroxymethyl groups in 4 was unambiguously established by X-ray- single crystal analysis. Tosylation of 4 and further reaction with benzylamine in toluene furnishes the tricyclic amine 5.
1. B.M. Mikhailov, Y.N. Bubnov, Organoboron compounds in organic synthesis, London, New York, Harwood Acad. Publishers, 1984.
123 P-46 i mill RU0410104 CONFORMATIONAL ANALYSIS OF l,3-I>IOXA-2-BORACYCLOALKANES
V.V. Kuznetsov
Ufa State Petroleum Technological University Russia, 450062, Ufa, Kosmonavtov sir., 1, e-mail: [email protected]
In accordance with NMR 'H results together with empirical (MM+) and quantum-chemical ab initio computations the potential energy surface of 1.3-dioxa-2-boracycloalkanes (the en- ergy differences between axial and equatorial forms [AE. kcal/mol] and barriers of ring inver- tion [AE . kcal/mol]) has been described. The conformational behavior of six-membered rings includes axial-equatorial equilibrium between two forms of sofa (S and S*) over 2,5-tnist- form (2,5-T).
-BR -O" -BR .BR
2,5-T- s*
BCM, O
R R1 method AE AE'
CH3 H MM+ 0.9 7.7 MP2/6-31G* 0.6 9.1 MP2/6-31G** 0.6 9.1
H CH3 MM+ 0.8 7.0 MP2/6-31G* 0.9 8.8 MP2/6-31G** 0.9 8.7 MP2/6-311G** 1.0 8.3 MP2/D95** 0.8 7.9
The conformational behavior of seven-membered rings also includes equilibrium between two forms of sofa.
liCH,
BCH3 BCH3 S 2.5.6-T The theoretical AE* of this process lays between 6.3 (MM+) and 9.0 (STO-3G) kcal/mol.
124 P-47 RU0410105 OF CYCLIC BORONIC ESTERS WITH NITRILES: A NEW SYNTHETIC APPROACH TO AMINOALCOHOLS
V.V. Kuznetsov
Ufa State Petroleum Technological University Russia, 450062, Ufa, Kosmonavtov str., 1, e-mail: kuznetsov@,oil.rb.m
Some new reactions of 5-7 membered cyclic boronic esters with nitriles have been described [1,2].
N
C-CHj + RB(OH)2 O IT R 40-60%
,011 o CH3CN ;B-R —•
CH3CN
cc>- —Ml-, 43-50° 0 CH. en.
-o O(CH2CH7CN)T \ E / en, 52% H C -O V—on 3 H3C CH, .on*
CH, CM, CIL 68-70% *• o(cn»K"n77cH7ocn-,aiv-\v O(CH7CH7OCH7CH7CN)7 • • • 21% H,C CH-, CH, -O (CH-,)-,C(OH)CN B-OH — *- -O " CH, CH, CH. CH, 10% A possible mechanism of this reaction has been discussed [3].
1. Kuznetsov V.V., Brysilovsky Y.E., Mazepa A.V. / Russ. J. Org. Chem. - 2000. - V.36, N12. P.1863. 2. Kuznetsov V.V., Brysilovsky Y.E., Mazepa A.V. / Russ. J. Heterocycl. Chem. - 2001. - N1.-P.135-136. 3. Kuznetsov V.V. / Theoret. Experimentl. Chem. (Russ.). - 2000. - V.36, N 3. - P. 159-161.
125 P-48 RU0410106 DUAL REACTIVITY OF (PHENYLBOROLE)RHODIUM COMPLEX
Dmitry A. Loginov, Pavel V. Kulikov, Dmitry V. Muratov, Pavel V. Pctrovskii, Zoya A. Starikova, Alexander R. Kudinov*
Xcswevcinov Institute of Organoelement Compounds, Russian Academy of Sciences, 1 !(JQQI Moscow, Russia, e-mail: [email protected]
Stacking reactions of (cyciohexylborole)cobalt complex CpCofC^BCy) with cationic half- sanuw ich iragments [(ring)M]"" have been shown to gi\'e u-borole triple-decker complexes [1]. ii": Me case of iphenyiboroicirhodiuiri complex 1 there are two possible places for electrophilic atiacl: h\ [iring)M]"" in = I. 2). Indeed, wr found thai depending on nature of the fragment either triple-decker (2 and 3) or arene (4 and 5) complexes are formed. The fragments h arene )Riij" lake an intermediate position yielding both triple-decker (6) and arene (7) complexes.
• 2+
2 + Rh M
2: M = Co B-Ph 3: M = Ir Rh
Ru
Rh
5 ' 6 " 7
The structures of complexes 1. 3-5. 6 (Rn - 1,3-5-Me;,) were determined by X-ray diffraction.
We thank the Russian Foundation for Basic Research (Grant No 00-03-32807).
!. A.R. Kucliixn. I).A. l,oiiino\. D.V. Muratov. I'.V. Pclrovskii. Russ. Client. Hull.. 2001. 50. 1332. 126 P-49 III RU0410107 SYNTHESIS AND CHARACTERIZATION OF SOME NOVEL TETRAHYDROBORATE COMPLEXES OF MAGNESIUM
V.D. Makhaev, A.P. Borisov, A.S. Antsyshkina*, G.G. Sadikov*
Institute of Problems of Chemical Physics of the RAS, Chernogolovka, Moscow Region, 142432 Russia, e-mail: [email protected] *N.S. Kurnakov Institute of General and Inorganic Chemistry of the RAS, Moscow, Leninskii pr. 31, 117907 Russia, e-mail: [email protected]
Magnesium tetrahydroborates are of interest as reductants with high content of active hydrogen. At present they are explored insufficiently, the structural data on the compounds are limited. We have shown that the reaction of MgCb with NaBH4 excess in 1,2- dimethoxyethane (DME) proceeds smoothly and gives sodium-free Mg(BH|)2i,5DME. unlike many other reactions of metal chlorides with NaBli; in DME, which give complexes
NaM(BH4)nxDME. Heating of Mg(BH4)21,5DME in a vacuum results in sublimation of
Mg(BH4)2DME. Mg(BH4)2 1,5DME gives anionic complexes with B14NBH4 or Ph4PBH4.
The structure of (Ph4P):[Mg(BH4]4 was determined by X-ray crystallography. The crystals of
(Ph4P)2[Mg(BH4)]4 are monoclinic: a=l 1.219(4), b=19.887(6), c=20.747(3) A, p -91.72 (6)°.
1 V=4627.2(4)A\ M = 381.2, F(000) =1624, pcaic=1.094 gW, |.iMo=0.14 mm" , Z=8, space group C2/c. Experimental data were obtained on an Enraf-Nonius CAD-4 diffractomcter
(/\.MoKu, graphite monochromator. 0/28 scan, 20 max=54°). The massive of reflexes contained an admixture of twinning reflexes. The structure was solved by a forward method on 4997 reflections, for 1275 of which F0>4G(F0). H atoms were partially determined from Fourier difference synthesis, remaining were placed in calculated positions. The non-H atoms were refined anisotropically. H atoms of BH4 groups participated in refinement with fixed tetrahedral parameters. Final values Ri=0.0825, wR2=0.2286, GOOF= 1.246 for 1275
3 reflections observed. Apmax =0.732, Apmin = -0.418e/A . Structural units of (Ph4P)2[Mg(BII4)]4
4 are the cations (Pl^P) and anions [Mg(BH4)]4~". Mg is surrounded by 4 BII4 groups posed on a tetrahedron. The BH4 groups possess different coordination to Mg atom: tv/o bidentatc
(MgHb 2.009; 2.108A) and two three-dentate (MgHb 2.206; 2.270 and 2.41 A) groups. Mg...B distances are 2.438(7) and 2.426(9) A, respectively.
127 P-50 RU0410108
2 UNCOMMON GEOMETRY OF THE CLOSO-DECABORATE ANION B,0Hi0 IN COMPLEX COMPOUNDS OF COPPER(I) AND SILVER(I)
E. Malinina, I.Polyakova, L.Goeva, N.Kuznetsov~ Kuniakov Institute of General and Inorganic Chemistry, Russian Academy of Science Lcniniskx pr., 31, Moscow GSP-J, 119991 Russia, e-mail: malinina(a)jgic.ras.ru
Complex compounds [Cu:(CH?CN)4BioHu,] (I) and Cu(CH3CN)3[AgBioHio] (II), in which the eloso-decaborate anions contain tetragonal faces, were synthesized and their crystal structures were determined.
Crystals (I) are built of the discrete [CU2(CH;CN)4B|(IH|,J] complexes. The distorted tetra- iiedrai coordination of the Cu~ ions is formed by two N atoms of the CH3CN1 molecules and two B-H groups of the BmHuf" anion. The anion coordinates the Cu ions by the edges of both the apical B(l)-B(2) and equatorial B(3)-B(6) belts. The Cu-B bond lengths are 2.25-2.29 A. The polyhedral anion is severely distorted on the side of the vertices that are not involved in metal coordination. The B(10)B(7) and B(10)B(9) bonds (1.50 and 1.55 A) are significantly shorter than the normal bonds, the B(4)-B(5) bond is ruptured (2.10 A), and the B(l)-B(4)-B(5)-B(8) fragment is flattened (the angle of folding about the B(4)-B(5) line is 13.6°).
+ Crystals (II) are built of the Ag(Bu,U]{))'x chains and the [Cu(NCCH3)3]"cations. The Ag ion is coordinated by six B-H groups from three B10H10"' anions. The symmetry of the closo-anion is C: Two symmetrically related edges of the apical belt (B(l)-B(2) and B(l')-B(2')) and the equatorial edge (B(5)-B(5') are involved in the coordination of three AgT ions. The Ag-B bonds are unequivalent: 2.547, 2.656 and 2.758 A for B(2), B(l) and B(5), respectively. Distortions of the polyhedron show themselves in the shortening of the coordinating B(l)-B(2), B(l')-B(2') and B(5)-B(5') edges to 1.57 and 1.63 the rupture of the B(2)-B(5) and B(2')-B(5') bonds (2.34 A) and the complete flattening of the B(1)B(2)B(5')B(5) and B(1')B(2')B(5)B(5') fragments (the angle of folding is 0.5°).
128 P-51 RU0410109
SYNTHESIS AND CONVERSION OF THE COMPLEX OF ALKALI AND ALKALIEARTH METALS TETRAHYDROBORATES WITH TRIETHYLENDIAMINE
A. I. Golovanova, N. N. Maltseva, N.T. Kuznetsov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiipr.31, Moscow, 119991, Russia, e-mail: dianntfyigic.ras.ru
A reaction of triethylendiamine (TEDA) C6H12N2 with alkaliearth metals tetrahydroborates in organic solvents (benzene, diethyl ether) was use to produce complex compounds
2M(BH4)n-TEDA, M= Li, Na, K, Mg, Ca, Sr; n=l-2. The compounds were characterized by chemical analysis, IR spectroscopy and DTA. The complexes transform to 2BH3TEDA in acetonitrile or upon heating. This compound was produced too by reaction TEDA with B2H6 in diethyl ether. We observed same transformation at mechano-chemical activation
2M(BH4)nL, L= cyclam, tetramethylcyclam.
Thermal decomposition of CbHi2N2-2BH3 under different conditions - in air, nitrogen or under vacuum was studied by differential thermal analysis (DTA). 2BH;,TEDA is oxidized at 250°C.
Then, at 350°C in argon or at 280°C under vacuum, the complex decomposes with partial evolution of hydrogen and diborane to produce a salt with the B^H,:""" anion after a series of thermal transformations.
129 P-52 RU0410110 LITHIUM AND SODIUM DERIVATIVES OF 11-VERTEX A7D0-CARBORANE ANIOINS
Vladimir I. Meshcheryakov, Gennadii V. Grintselev-Knyazev, Pavel V. Petrovskii, Alexander R. Kudinov
NesmevanoY Institute of Organoelcment Compounds, Russian Academy of Sciences, 119991 Moscow. Russia, e-mail: [email protected]
Lithium and sodium derivatives of 11-vertex /z/av-earborane anions are widely used as starting materials in metallacarborane chemistry. Their structures were determined for the first time in this work by X-ray diffraction. Lithium derivatives have sandwich structures. Sodium derivatives have dimeric or polymeric structures, in which each metal atom is simultaneously bonded with two earborane ligands.
' c V It was shown by means of the H and B NMR spectroscopy that these compounds usual!) dissociate in strongly coordinating solvents. 130 P-53 RU0410111 DIRECT ASYMMETRIC SYNTHESIS OF AN0-CARBORANE DERIVATIVE S. K. Moiseev, R. V. Lebedev, M. M. IP in, V. A: Davankov, V. N. Kalinin A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str. 28, 117813 Moscow, Russian Federation. Fax: +7 (095) 135 6549, e-mail: vkalinfojineos.ae.ru The optically active carborane derivatives bearing an asymmetric carbon atom in the side chain are prepared by attaching the carborane moiety to chiral substrates [1]. Methyl esters of (2-R-o/t/?o-carboranyl)acetic acids are known to have rather high CH-acidity of CH2 group. They can be allylated at this position with allyl carbonates in the presence of a palladium catalyst [2]. Here we report the direct asymmetric synthesis of the carborane derivative 3 by a Pd- catalyzed allylation of ester 1 with allyl methyl carbonate 2. Phosphites of the formula (ArO)2P-O-CH2-CHR/-N=CHR and compound 4 were used as the chiral ligands (L*) and (;/- C3H5PdCl): as the pre-catalyst. Ph I 2 OCO.Me PhC—CCHCOO.Me PhC— C \ N 4 Ph The phosphite ligands allowed to obtain the cross-coupling product 3 in up to 98% yield. But the ee's did not exceed 32%. The highest asymmetric induction was provided by 4 as the L* (48% ee, 44% yield). This is rather high enantioseleetivity for the allylation process leading to a fonnation of a new chiral center at the nucleophile (not allyl!) carbon atom. 1. A. H. Soloway, W. Tjarks, B. A. Barnum, F.-G. Rong, R. F. Barth, 1. M. Codogni, and J. G. Wilson, Chem. Rev., 1998,98, 1515-1562. 2. S.C. Shim, J.G.Shim, S.Y. Chae, S.Y.Lec and V.N. Kalinin, J. Organomet. Chem., 1993, 443, C22. ,31 P-54 mill RU0410112 NEW TRIPLE-DECKER COMPLEXES WITH A CENTRAL BOROLE LIGAND Dmitry V. Muratov", Denis N. Mavrinskya, Pavel V. Petrovskiia, Zoya A. Starikovaa, Gerhard E. Herberichb*, Alexander R. Kudinova* a Nesmevanov Institute of Organoelement Compounds, 119991 Moscow. Russia, e-mail: [email protected] h Institut fur Anorganische Chemie, Technische Hochshule Aachen, 52056 Aachen. Germany, e-mail: gerhard.herberichiaac.nvth-aachen.deS It wa.-. shown earlier thai (borole (cobalt anion [(CiFLBPh^Co]' reacts with metallaelectrophiles to form triple-decker complexes with a central borole ligand [1]. We found that reactions of rhodium analogue 1 with some cationic metallaelectrophiles, generated from their labile complexes, lead to triple-deckers 2-5 with good yields. M M Rh Rh [(ring)M]: 2 Cp*Fe 3a,b CpRu, Cp*Ru 4 C4Me4Co 5 Codlr 3a The structures of compounds 3a,b were confirmed by X-ray diffraction study. I. G.H. Herberich, B. Hessner, and R. Saive, J. Organometal. Chem., 1987,319, 9. [32 P-55 RU0410113 INTERACTION OF UNDECAHYDRODECABORATE(l-) ANION BioHu WITH NUCLEOPHILIC REAGENTS V.Mustyatsa, K.Zhizhin, N.Votinova, I.Polyakova, N.Kuznetsov Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science Leniniskypr., 31, Moscow GSP—1, 119991 Russia, e-mail: zhizhintyigic.ras.ru Interaction between the undecahydrodecaborate anion BioHn" and nucleophilic reagents L (L = MeCN, THF, 1,4-dioxane, morpholine) is studied. The reaction proceeds by the regioselective mechanism and results in the formation of only one of all the possible isomers, namely, the equatorially monosubstituted 2-LB10H9" closo-decaborate anion. It is suggested that the addition of L to the polyhedron proceeds upon the detachment of HT from the equatorial site. The substituted polyhedral anions are characterized by IR and NMR spectra and X-ray diffraction. "••fy, B10H9NCCH3" B10HgO(CH2)4" 133 P-56 RU0410114 THE FIRST SYNTHESIS OF ADENOSINE CONTAINING CARBORANE MODIFICATION ATTACHED TO SUGAR RESIDUE M. Kwiatkowski1, A. Olejniczak2, A. Semenuk1, and Z. Lesnikowski 1 Institution f Genetik och Patologi, Rudbeck Laboratoiy, Uppsala Unixersitet, Uppsala, SE- 751 85, Sweden, e-mail: [email protected], [email protected]; ' Laboratoiy of Molecular Virology and Biological Chemistry, Center for Microbiology and Vii'ologv PAS, Lodz 93-232, Poland, e-mail: [email protected], zlesnik(a cmiwpan. lodz.pl The original rationale for the design and synthesis of boron-containing nucleosides is their potential application as boron rich carriers for BNCT [1]. In addition, boron cage is being pursued recently as lipophilic pharmacophore for antiviral nucleosides and other biomolecules [1,2]. Most carborane-modified nucleosides belong to pyrimidine series. Though, synthesis of a carborane-containing purine nucleoside was also attempted, the 2-o-carboranyl-inosine precursor could not be deprotected [3]. In this communication we present the first synthesis of adenosine containing carborane modification attached to sugar residue at 2"-position. The 2'-<9-[3-(/>carboran-l- yl)propyl]adenosine was synthesized in the reaction of 3\5'-O,0-(tetraisopropyldisiloxane- 1,3-diyl)-A/6-benzoyl-2'-O-methylthiomethyladenosine with 1 -(3-hydroxypropyl)-/?-carborane. Next the disiloxane protecting group was removed with TBAF in THF solution, and benzoyl group was removed with concentrated aqueous ammonia solution. Deprotected 2'-O-[3-(/>- carboran-l-yl)propyl]adenosine was characterized using chromatographic and instrumental methods. Supported by the Polish Committee for Scientific Research (KBN), grant 6 PO5F 023 20p02. 1. Lesnikowski Z.J., Shi J., Schinazi R.F., J. Organomet. Chem., 581, 156-169,(1999). 2. Yamamoto K., Endo Y., Bioorg. Med. Chem. Lett., 11, 2389-2392, (2001). 3. Yamamoto Y., Seko T., Nakamura H., Heteroatom Chem., 3, 239-241 (1992). 134 P-57 RU0410115 C-Cc BONDING IN Q-SUBSTITUTED l,2-DICARBA-c/ Markku R. Sundberg,* Sari Paavola*, Francesc Teixidor/ Clara Vinas," Bernard Silvi,a Rolf Uggla,* Raikko Kivekas* 'Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, Finland; 4ICMAB, CSIC, Campus U.A.B., Bellaterra, Catalonia, Spain; ° Laboratoire de Chimie Theorique, Universite Pierre et Marie Curie, Paris, France, e-mails: [email protected], [email protected], teixidor@icmab. es, [email protected], [email protected], [email protected], [email protected] Density Functional Theory was applied to X C X-Q-Q-X :c-cc X-Q.-Q optimize the structures of 14 differently H 1.625 116.14 0.08 Cc-substituted 1,2-dicarba-c/oso- AsH2 1.656 115.67 8.83 dodecaboranes at the B3LYP/6-31G* level CH3 1.663 118.70 0.00 of theory. Results agreed very well with F 1.665 114.96 0.04 the earlier results of crystal staicture SeH 1.668 114.67 4.53 analyses, conforming that different Br 1.682 118.21 0.03 substituents at Cc atoms effect wide PH2 1.689 116.84 6.04 variation in the Cc-Cc bond distance. As Cl 1.694 118.11 0.07 the Cc-Cc distance increases from 1.625 to OH 1.771 115.62 0.00 1.882 A, the bonding nature changes from SH 1.815 118.36 0.06 covalency via protocovalency into closed- NH2 1.882 114.85 0.02 shell interaction. Selected geometrical parameters [A, °J for optimised compounds. X - Cc substituent. Gradient-corrected density functional theory applied to l,2-diphosphino-l,2-dicarba- c/oso-dodecaborane, 1,2-(PH2)2-1,2-C;>BIOHIO, and its PdCl: complex indicated that the plasticity of the five-membered chelate ring is steered by the atoms or groups connected to phosphonis. Plasticity is seen in variance of the Cc-Cc bond lengths, P-Cc-Cc angles and P-Cc-Cc-P torsion angles. 135 P-58 RU0410116 A NEW METALLACARBORANES OF RUTHENIUM AND RHODIUM Dmitry S. Perekalin, Stanislav S. R)Tiin, Konstantin A. Lyssenko, Gennadii V. Grintselcv-Knyazev, Pavel V. Petrovskii, Alexander R. Kudinov* Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russia, e-mail: [email protected] New ruthena- and rhodacarboranes 1-3 were synthesized by interaction of nido-carborane anions with (ring)MCln complexes. © Rh S \ O V; 1 0 * ( Ru // /; Ru Ru ' f \ ' 'V--.. Oc OB Their structures and properties were compared with those of the corresponding metallocenes. For example, complex 3 reacts with [Cp*Ru]* fragment to give polyhedral expansion product 4, while Cp*iRu react with the same fragment to give triple-decker complex [Cp*Ru(ji- fp*)RuCp*l'. 136 P-59 RU0410117 CRYSTAL STRUCTURES OF BIS(DICARBOLLIDE) Co(III) AND Ni(III) 2 COMPLEXES WITH CATION IM(Phen)3| ^ T.M. Polyanskaya, V.V. Volkov, M.K. Drozdova Institute of Inorganic Chemistry SB RAS, Ac.Lavrentiev av., 3, 630090, Novosibirsk, Russia, e-mail: [email protected] The self-assembly of different building blocks is currently of considerable interest. The potential applications of crystal macroscopic physical properties are defined by the intermolecular electronic interactions present in the solid state. We have carried out single-crystal analysis at room temperature of the title compounds with II I M m formulaes [M Phen3][M "(B9C2Hll)2]2.n(CH3CN), where M = Cu, Ni; M = Co, Ni; Phen = 1,10-phenanthroline, n = 14-3. The formulaes are established by X-ray study. The central M11 atom is coordinated by six nitrogen atoms from three of bidentate Phen molecules as a distorted octahedron in all compaunds. Cu-N distances range from 2.076 to 2.148 A, the mean 2.142(2) A, for compound (I) with M1" = Co, and from 2.059 to 2.176 A. the mean 2.111(5) A, in compound (II) with M1" = Ni. Ni-N distances range from 2.078 to 2.093 A; the mean 2.083(3) A, in cation of compound (III) with M1" = Ni. Intraligand N-M-N angles vary from 77.7 to 78.8°. the mean 78.5°; 77.8 to 79.7°, the mean 78.7°; and 79.4 to 79.7°, the mean 79.6°, in I, II and HI, respectively. The nearest MI"...MI" separations are 7.075A in I, 7.065; 7.213; 8.897 A in II and 6.959; 7.044; 10.899 A for two crysta'lographically unique [M'"(BQC;;HII)2]~ anions in II and III, respectively. The nearest separations between central cation and anion atoms are 8.241 A in I: 7.824; 8.164 A in II; 7.595; 9.518 A in III. The anions have the expected overall geometry in which two {MmBqC:} icosahedra are linked via a common M1" atom. The arrangement of the -C:- groups in the one crystallographically unique bis(dicarbollide) anion of I corresponds to quasi-gauche- configuration. Each of the two nickel anions in compounds II and III has its own disposition of the dicarbollide fragments. The cations and anions are packed so that there are channels with irregular form in which guest acetonitriie molecules are included: n=2; 1 and 3 for I, II and III, respectively. Acetonitriie nitrogen atoms participate in host-to-guest interactions with Phen ligands through contacts N...H-Cp|Kn with d(N...H) that are less than the sum of the van der Waals radii. 137 P-60 RU0410118 FEATURES OF MOLECULAR STRUCTURE OF 6,9-(PPhj)2B,oH,2 T.M. Polyanskaya, V.V. Volkov, M.K. Drozdova Institute of Inorganic Chemistry SB RAS, Lavrentiev av., 3, Novosibirsk, Russia, e-mail: [email protected] Preparation of title complex I has been made more than 40 years ago [1,2] but information about its structure is absent in the Cambridge Strutural Database at present. In this work, molecular complex I (shown in the figure) has been studied by X-ray single crystal crystallography at room temperature as fixed in I-2[HCON(CH?)2]-H:O compound (II). Crystals of II suitable for X-ray analysis were obtained b\ polythermal cn'stallization I from dimethylformamide in the presence of water vapour. Formula II is established by X-ray studv. Complex I has the crystallographically imposed Cs symmetry. The geometry of the Bio fragment has not undergone a substantial modification and is typical of such 6,9- bis(ligand)decaborane species. The geometry around P is approximately tetrahcdral. The interatomic distances (A) are: B-B 1.732(5)-1.896(8), B-P 1.911(3), P-C 1.804(3)^1.817(3), C-C 1.324(7)^-1.404(6). The orientation of the phenyl groups is given by the torsion angles: B,,-P-Ci-C2 = 28.3; B(,-P-C7-Cx = 71.7 and B6-P-C,3-Ci4 =10.7°. 1. 1 lawthome M. F., Pilochclli A. R. J. Am. Chem. Soc. 1958, 80, 6685. 2. Pace R. J., Williams J., Williams R. L../. Chem. Soc. 196/, 2196-2204. 138 P-61 RU0410119 SYNTHESIS AND ENANTIOSELECTIVE REDUCTION OF BENZOFURYL KETONES Andrzej Prewysz-Kwinto, Agnieszka Tafelska-Kaczmarek, and Marek Zaidlewicz Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland, e-mail: zaidlevi@chem. uni.torun.pl Benzofurans substituted at the 2- and 3-position exhibit diverse pharmacological activity and are the subject of constant interest [1,2]. Enantiomerically pure derivatives, such as alcohols, are highly desirable. In this study, enantioselective reduction of various 2- and 3-benzofuryl ketones with (-)-i?-chlorodiisopinocampheylborane (DIP-chloride) has been examined. R? R3 I COPh Me 5-Me 6 Me COCII:Ph H 2 Me COPh H 7 COCH.Ph Me 7-CI 3 CH.COPh H H 8 Me COCH,Ph-/>OMe H 4 CH2COPh-/?-F H H 9 H-Bu COCH:Ph H 5 Me CH,COPh H 10 COCH,Ph H H The reduction of 2- and 3-acetylbenzofurans with DIP-chloride gave the corresponding alcohols of 90-91% ee. Their configuration was established by X-ray analysis of /7-nitrobenzoates. Benzofuryl benzyl ketones 6-10 were also reduced with comparable enantioselectivity (88-93% ee). In contrast, benzofurufryl aryl ketones 3-5 reacted with much lower selectivity producing alcohols of 30% ee, and benzofuryl aryl ketones 1 and 2 were not reduced by the reagent. A convenient synthesis of 3-acylbenzofurans and other 3-substituted derivatives, not readily accessible by other methods, has been developed. Thus. 3-methylbenzofuran was oxidized with selenium dioxide to 3-formylbenzofuran. The reaction is highly solvent dependent. The aldehyde is a useful intermediate in the synthesis of 3-acylbenzofurans. 3-cyanomethyl-, 3-hydroxymethyl-, and 3-chloromethylbenzofuran [3]. A general synthesis of 3-((o-alkenyl)benzofurans from the same aldehyde precursor has been developed. 1. D. N. Li, P. M. Pritchard, S. P. Hanlon, B. Burchell, C. R. Wolf, and T. Friedberg, J. Pharmacol. Exp. Thcr., 1999, 289, 661. 2. T. K. Vinh, M. Ahmadi, P. O. Lopez Deigado, S. Fernandez Perez, H. M. Walters, J. H. Smith, P. J. Nicholls, C. Simons, Bioorg. Med. Chem. Lett., 1999, 9, 2105. 3. M. Zaidlewicz, A. Chechlowska, A. Prewysz-Kwinto, and A. Wojtczak, Ileterocycles, 2001, 55, 569. 139 P-62 mill RU0410120 PLATINUM(O) CATALYZED DIBORATION OF ALKYNYLBORONATES AND ALKYNYLPHOSPHONATE WITH B1S(PINACOLATO)DIBORANE(4) Hijazi Abu Ali," Abed El Aziz Al Quntar.8 Israel Goldberg,1'Morris Srebnik*3 '' Department of Medicinal Chemistry and Natural Products, School of Pharmacy, Hebrew University in Jerusalem, Jerusalem. Israe;. h School ofChemistiy, Tel-Aviv University, Ramat-Aviv 69987, Tel-Aviv, e-mail: Israel.msrebni(cvmd.huji.ac.il The Platinum(O) catalyzed diboration addition reaction of bis(pinacolato)diborane(4) [(Me4C:O;)BB(O2C:Me4). 1] with various 1 -alkynylphosphonates and l-alkynylboronates3a- d gave the desired novel cis-! .2-diboronated vinylphosphonates and trisboronated alkenes 5a, 5b and 5c. 5d respectively, in high yields. No detectable amount of the desired trisboronated alkenes 5c and 5d were isolated when the alkynylboronate was immediately added to a toluene solution of the catalyst and bis(pinacolato)diborane(4) followed by stirring overnight at 80 °C. Under these conditions, cis-],2-diboronated alkenes were obtained in 100O/o conversion yields. Only after changing the reaction conditions were 5c and 5d obtained in high yields. The structure and configuration of the new compounds have been fully characterized by *H, I3C.3I P and nB NMR, GCMS, elemental analysis and single-crystal X- ray structure determination. The structure of 5d was found to be fully isomorphous to that of 5c. with the C^H^ ring located in place (and similarly disordered about the 2-fold symmetry axis) of the C4H9 residue. O O / 3h/80°C Ph5l\ /P1^ overnight/80 °C ^ / R: y &--B - Pul'l'h,l4 >• Pi * R,-C^C—R, *• C=C o 0 >i-i— OB7 XBO 3 " toluene °B Vo 1 /\ O O / ^1 0 O ^ 5a d 3a Rp-CjH,,. R- ' P(O)(OC2H5)2 " 31) R, C,,IU. R2 P(O)(OC:H5)2 3c R, C4II,,. R," Bpin 3d: R, C6H5, R2 Bpin +A. A. Q. Acknowledges a travel grant from the David R. Bloom Center for Pharmacy at the Hebrew University. 140 P-63 RU0410121 CARBORANE-CONTAINING NEUTRON ABSORBERS AS TECHNOLOGICAL COMPONENTS OF SAFE PROCESSING OF FISSILE MATERIALS SOLUTIONS Edouard V. RENARD Federal State Unitary Enterprise "Bochvars All-Russia Scientific-Research Institute of Inorganic Materials " (VNIINM), Russia, Moscow, 123060, POB 369, e-mail: renar(w,bochvar.ru The only technological complex decision of nuclear safety and productivity for hydrometallurgical operations of processing of fissile materials (U, Pu) can be achieved by use insoluble in water (boron) carborane-containing solvents (extractants, diluents and sorbents - ionites). Is investigated and the high chemical and radiation stability of three carborane [B10H10C2H2] isomers in a role of diluents of tri-n.buthylphosphate (TBP) - classical radiochemical extractant U and Pu is confirmed. Besides boron-containing diluents, - for the mentioned purposes it is possible to use extractants, similar on structure and functional groups TBP, but with entered in their structure carborane isomers and their derivatives. By reaction of condensation of chlordibuthlphosphate with o-carboranemetylol - o-carboranilenemetyloloxydibuthylphosphate has been preparated. This extractant is similar TBP and selective in relation to fissile materials. Were modified by boron analogues of widely used in nonferrous metallurgy and radiochemical practice anionites and cationites — vinylpyridine-divinylbenzene and styrene-divinylbenzene types, in particular, boron-containing cationits and anionites on a basis co-polymers (matrixes) styrene or vinylpyridine (and its derivative) with divinylbenzene and containing the carborane isomers nonsaturated derivatives. 23 samples boron-containing anionites are tested. All of them have found out satisfactory sorption ability in relation to Pu (IV) and good selectivity to this ion in comparison with U (VI). From the investigated compositions best sorption properties has found out weak-base boron- pyridine anionite, produced on reaction three-polymerization of 4-vinylpiridine, isopropenyl-o- carborane and divinylbcnzene. The best ability to polymerization has shown isopropenyl-o- carborane in reactions both co-polymerization and homo-polymerization. 1. E.V.Renard. Homogeneous neutron absorbers as technological components of processes of management of nuclear fuel, "Sov. Atomic Energy", v.72, No 5,1992, pp.444-451 141 P-64 RU0410122 FORMATION OF BORON-NITRIDE STRUCTURES BY THERMOLYSIS OF BORANES COMPLEXES WITH NITROGEN-HYDROGEN BASES OF LEWIS V.V.Zakharov, A.S.Rozenberg, G.N.Nechiporenko Institute of Problems of Chemical Phisics RAS Chenwgolovka, Moscow Region. 142432 Russia, e-mail: vzakh@,icp.ac.ru On the recent years the concern to the preparation and analysis of properties of boron- nitrogen-hydrogen (BNH) compounds as synthetic precursors of a boron nitride, of boron- nitrogen-containing fibres and ceramics has increased in the light of their possible practical usage. In this article the analysis of experimental reserches of a thermal solid phase decompo- sition of BNH systems were conducted under the compositions when the atomic [N]/[B] ratio >1: donor- acceptor nitrogen-hydrogen complexes of boranes (aminc- and hydrazine-boranes, AKBH.O-i n N:H4) and high boron hydrides (B;,H|(I-2NH.;. Bp.Hi^NH.v N;H4 ), including the complexes in amine and hydrazine mediums (B|()H|i,-2NH;, + xNH^, N2H4). The models of possible initial routes of thermal conversion of BNH compounds in the solid phase and the reasons of absence of direct dissociation of these complexes on a donor- acceptor B<—N bond have been reviewed. The evalution calculations of activation parameters of these processes have been conducted and the most probable channels of transformation have been detected. The possible directions of formation of boron-nitridesimilar structures at deep stages of thermal conversion of Lewis boron hydrides complexes resulting in the formation of boron nitride structural precursors have been analysed. The problems of rearrangement of boron- hydrazine fragments to boron-amine fragments with scission of N-N bond during the thermo- lysis of hydrazinoboranes were discussed. On the basis of principles of the topological de- scriptions of a boric skeleton the construction of the possible schemes of boron-nitridesimilar structuresformation in the process of destructive nitriding high boron hydrides by nitrogen- hydrogen Lewis bases. The thcrmochemical analysis of BNH fragments arising during these transformations has been conducted. The energy parameters of three basic successive reac- tions of the interaction of hydrazine with BioHi(,.2N]L were estimated: the formation of a do- nor-acceptor B<—N bond, the formation oi covalcnt B-NH2 bond and the formation B-NH-B bonds with the evolution of hydrogen. 142 P-65 RU0410123 NEW MIXED-METAL TRIPLE-DECKER COMPLEXES WITH 2,3-D!HYDRO-l,3-DIBOROLYL LIGAND Vyacheslav Scherbanab, AlcxandcrRomanova, Pavel Petrovskii\ Zoya Starikova3, Alexander Kudinov*a, Walter Siebert*b a Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russia, e-mail: [email protected] b Anorganisch-Chemisches Institut der Universitdt Heidelberg, 69210 Heidelberg, Germany, e-mail: ci5@ix. urz. uni-heidelberg. de The ability of the 2,3-dihydro-l,3-diborolyl ligand 1 to form strong bonds on bifacial coordination with metal atoms is well-known as many triple-decker complexes with 1 in the bridging position have been reported [1,2]. In the present work we have reacted the cationic half-sandwich fragments [(ring)M]+ with the complex anion 2 in order to synthesize the triple- deckers 3-6. For instance, complex 3b was isolated in 70% yield and characterized by X-ray structure analysis. (ring)M: 3a,b CpRu, Cp*Ru 4a,b CpFe. Cp'Fe I 5 (C4Me4)Co 6 (C3B2Me5H)Rh However, not all reactions led to the desired products. For example, instead of the formation of 6, proton transfer between reactants was observed. As a result of this work, some conclusions about electronic and sterical factors influencing the course of the reactions of this type can be made. 1. W. Siebert, Angew.Chem.. Int. Ed. Engl. 1985, 24, 943. 2. W. Siebert, Adv. Organomet. Chem. 1993, 55, 187. 143 P-66 RU0410124 THIN SOLID FILMS OF THE PSEUDOISOCYAN1NE DOPED BY CLUSTER BORANE DERIVATIVES FOR NONLINEAR OPTICS Vladimir V. Shelkovnikov , Zoja I. Ivanova , Natalja A. Orlova , Vladimir V. Volkov , Maria K. Drozdova" Alexander I. Plekhanov , Roman V. Markov Novosibirsk Institute of Organic Chemistiy, 9 Academician Lavrentjev Ave., Novosibirsk 630090, Russia; Institute of Inorganic Chemistiy, 3 Academician Lavrentjev Ave., Novosibirsk 630090, Russia; "institute of Automation and Electrometry, 1 University Ave., Novosibirsk 630090. Russia The optical and nonlinear optical properties of low-dimensional molecular systems with continuous structure such as J-aggregates of the c)anine dyes are intensive studied at present time. Modern interest to the pseudoisocyanine (PIC) J-aggregates is caused by their large cubic susceptibility at picoseconds relaxation times. The influence of the additives with high space electron delocalization such as cluster borane derivatives on the PIC J-aggregate formation in thin solid films was studied in this work. The number of used high boranes and carboranes dopands is listed bellow. 2- PIC-I + L 2 2 2 L=Bl0H10 \B,2Hp -, B20H18 -, 0 [Ni(B9C2Hn)2] , Ni(l,2-B9C2Hn)2\ B9C2H,2", Co(l,2B9C2Hn)2', l,7-BioC2H]2, 1,2-BIOC2HI2, a - \ / - a~ Ni(B9C2H,,)2- PIC It was found that the best stability and the nonlinearity of the films was observed for the PIC dye doped by the cluster borane derivatives K^BioHio or [NifBgC^Hn^]0. They stimulate the J-aggregation of the PIC dye in thin solid films and thus allow to obtain the thin (20-30 nm) J- aggregated films with high optical quality. The films possess a high thermal stability and allow to control optical nonlinearity of J-aggregates for the first time. The nonlinear optical properties of the obtained films were measured by Z-scan and pump-probe methods. The main obtained nonlinear parameters are: cubic susceptibility ~ 10"^ esu, threshold of the laser destruction ~ 5MW/cm:, nonlinear absorption coefficient - -5'10"2cm/W. The work was supported by grant NWO-2001 and RFBR grant 02-03-33336 144 P-67 RU0410125 ELECTROCHEMICAL SYNTHESIS OF HALOGEN-SUBSTITUTED CARBORANE DERIVATIVES V.L.Shirokii. A.V.Bazhanov, D.A.Rudakov, A.N.Ryabtsev and N.A.Maier Institute of Physical Organic Chemistry of the Belarus National Academy of Sciences, Surganov st. 13, 220072 Minsk, Republic of Belarus, e-mail: shirokii(cv,ifoch.bas-nel.b\. On electrolysis of the tetramethylammonium bis-dicarbollyliron salt with DC current in absolute methanol in the presence of sodium bromide, a mixture of mono- and dibromo-bis- dicarbollyliron salts is formed. The monosubstituted salt yield was 44 %. As the electrolysis proceeded further, the yield of monosubstituted salt decreased (down to 23 %), whereas that of disubstituted salt increased (up to 25 %). A thermostated electrolyzer featuring a platinum anode and a nickel cathode was used. The electrolysis was conducted at 50° C. Monitoring of conversion level of the starting compound, as well as purity testing of the products isolated, were performed by means of cyclic voltammetry (CV). Composition and structures of the obtained compounds were confirmed by elemental analysis, as well as by CV, IR and mass spectral data. The structure of monobromo-substituted bis-dicarbollyliron salt was confirmed by X-ray structural analysis. Electrochemical halogenation of a bis-dicarbollylcobalt salt using LiCl, NaBr or Nal as supporting electrolyte leads to the formation of the respective 8,8'-diha!ogenated derivatives of bis-dicarbollylcobalt in yields of 45-64 %. The structures of dihalogenated compounds were confirmed by elemental analysis, as well as IR. UB NMR and mass spectral data. II where: M = Na, X = Br, I; M = Li, X = Cl.; Me=Fe,Co. With the purpose of development of an alternative approach to the synthesis of halogen- substituted bis-dicarbollyl derivatives of transition metals, electrochemical halogenation of potassium dicarbadodecahydroaundecaborate (1) was studied. The halogenation was conducted under conditions similar to those described above. Electrochemical iodination and bromination of the salt (1) led to the formation of 9(1 l)-monohalo-substitutcd undecaborates, the structures of which were confirmed by elelmental analysis, as well as IR, "B NMR and mass spectral data. Yields of the monoiodinatcd salt reached 83-95 %; these of the monobrominated salt were somewhat lower - up to 60 %. The study has been financially supported by INTAS (grant N» 99-00806). 145 P-68 RU0410126 ELECTROCHEMICAL SYNTHESIS OF BIS-(9-DIMETHYLSULPIIONIO-7,8- DICARBOLLYL) -IRON AND -COBALT DERIVATIVES V.L.Shirokii. A.V.Bazhanov, N.I.Nikishkin, A.N.Ryabtsev and N.A.Maier Institute of Physical Organic Chemistiy of the Belarus National Academy of Sciences, Surganov st. 13, 220072 Minsk, Republic of Belarus, e-mail: [email protected]. By electrolysis of nido-9-dimethylsulphonio-7.8-dicarbaundecaborane [nido-9-(Me2S)-7,8- C2B^H-,i] (1) in an electrolyzer featuring a sacrificial iron anode. bis-(9-dimethylsulphonio- 7.8-dicarboilyl jiron(ll) (2) was prepared in yields reaching 66-89 %. Due to chirality of the initial carborane (1), three isomers of the compound (2) were formed: a racemic pair of enantiomers (DD/LL) and a meso-form. The meso-form precipitated in the course of electrolysis, thus facilitating the separation of isomers. -r- .-A-. O.IN lljNd. Clltf'N " iiL WIf, " -^^.^'^ , Nlc2S Kk'drolNsis ^1.1^/ ' sv«i-\^ MKSO I)|) Structures of the obtained compounds were confirmed by IR, 'li NMR and mass spectral data. Cyclic voltammetry studies revealed that the compound (2) undergoes a reversible one- electron oxidation at a potential of ^0.46 V (vs. SCE"). H NMR spectrum of the DD/LL form features two pairs of singlets: in the ranges of 2-3 ppm (M^S-) and 5-7 ppm (carborane C-H). Characteristics of isomers of the compound we have prepared agree with those described in the literature. By electrolysis of carborane (1) in an electrolyzer featuring a sacrificial cobalt anode (acetonitrile solvent, tetramethylammonium bromide supporting electrolyte, temperature 40° C. current density 25 mA/cirf), a product of formula [(9-Me2S-7,8-C2B9Hio)2Co]Cl was obtained. Yields of this compound amounted to 65 %. On combined electrolysis of the carborane (1) and unsubstituted potassium dicarbadodecahydroundccaborate in an ciectrolyzcr featuring a sacrificial cobalt anode, a compound of formula (9-Me2S-7.8-C2BlJlio)Co(C2B.;l In ) was obtained. The study has been financially supported by INTAS (grant JVL> 99-00806). 146 P-69 RU0410127 BIOCIDAL SCREENING OF TETRACOORDINATED BORON COMPLEXES Vijay P. Sini*h' and R. V. Singh" Department of Sciences, Molepolole College, (University of Botswana), Private Bag 008, Molepolole, Botswana. Department of Chemistry, University oj'Rajasthan, Jaipur 302004, India. E-mail: Tctracoordinated boron complexes have been synthesized by reacting Oxygen. Nitrogen and Sulfur donor ligands with a variety of simple boron compounds as starting material. The reactions were carried out in 1:1 and 1:2 molar ratio under completely dry conditions by using dry benzene or toluene as a solvent medium for the reactions. The by-products such as water and ethanoic acid were removed azeotropically. The products were characterized by elemental analysis and popular spectral studies such as IR, lH NMR, I3C NMR, I!B NMR and electronic spectra. A number of ligands and the boron complexes derived from them were tested for their toxicity against a number of bacteria and fungi. Cultures of£. coli and P. cepacicola both Gram Negative bacteria and those of X. campestris, S. aureus, B. subtilis all Gram Negative bacteria were prepared and disc diffusion technique [1] was used to observe the zone of growth inhibition of the colony around the the discs impregnated with the solution of compound to be examined. For the antimycotic activity poisoned food technique [2,3] was employed by using F. oxvsporium, M. phoseolina, C. albicans, C. neoformans and A. fumigatus as test fungi. The growth inhibiting tendency of the ligands and their boron complexes were also compared with a conventional fungicide and a baetericide. The increseau toxicoty of the complexes over the ligands was interpreted in terms of complexation and donor atoms available in the ligands. The results are quite motivating to explore much more in this direction. 1. V. P. Singh, et al. Main Group Metal Chem., 1991, 14(2). 81-88. 245. 2. T. Pandey, V. P. Singh and R. V. Singh, Main Group Metal Chem., 1998, 21 (4), 185 - 191. 3. T. Pandey, V. P. Singh and R. V. Singh, Main Group Metal Chem.. 1999, 22 (3), 315- 320. 147 P-70 nun RU0410128 DIBORANE REACTIONS AND SYNTHESIS INITIATED BY CO2- LASER PULSE IRRADIATION A.N.Skachkov FSUE SRC RF GNlICIiTEOS, 38 Slwsse Entitziastov, Moscow 111123, Russia, e-mail: eos@,eos.incotrade.ru Prospects of IR laser wide application in chemical technology are considerably related to the possibility of laser-chemical processes occurrence under reagents pressures close to atmospheric ones and moderate ( up to 10 W cm ~~ ) irradiation intensities. Thermal component of irradia- tion makes a major contribution under such conditions. The dynamics of laser heating and absorbing gas cooling was analyzed. This analysis demonstrated peculiarity of pulse (10"' - 10"("s) IR laser irradiation thermal effect, consisting in homogeneous reagent heating up to 104 K at the rate of 106 K' s ~\ cooling of reaction products, readiness for reaction volume (0.1 - 100 sm1) control and precise metering of laser energy. This peculiarity has been successfully implemented in FSUE "GNIIChTEOS" on the example of la- (> ser chemical (pulse 10"' - 10" s, CO"-laser, ?J=10.6 urn) reactions of B2H6. Results of experimental study of high temperature (T - 1000 - 2000 K) laser-chemical B^IL synthesis (BHCH in BfL hydrogenation by hydrogen, monosilane and methane as well as B4C and B reactions evaporated by laser irradiation under hydrogen environment are presented. Homogeneous conditions of laser-chemical reaction initiating allowed high-temperature B2H6 (BHCI2) synthesis with quantitative yield. Laser - chemical thermal (T - 1000 K) B6H6 dissociation and its reactions with C2H2 and x were analyzed: • BsHq ; B10H16 ; H2 CO-* - laser B2H6 ->• closo - carboranes 3,4,5 iC4H8 • B2H4 (i C4H9 )2 All the investigated laser chemical processes are characterized by sharp threshold de- pendence on reagent pressures and irradiation intensity, they are accompanied with fluorescence in visible irradiation range, single - channel directivity of the chemical process and there are no polymeric condensed boron - containing products in the reaction products. Thermodynamic and kinetic aspects of the investigated processes are analyzed. Laser chemical processes scaling and practical implementation are being looked upon. 148 P-71 RU0410129 COBALT(I)-CATALYZED NEUTRAL DIELS-ALDER REACTIONS OF BORON CONTAINING DfENES AND D1ENOPHILES Gerhard Hilt , Konstantin Smolko Department of Chemistry, Ludwig-Maximilians-Universitdt Miinchen, Butenandtstr. 5-13, Building F, 81377 Miinchen, Germany, e-mail: Gerhard.HiltCdcup.uni-muenchen.dc Dialkoxyethynylboronates [1] and dialkylethynylboranes [2] are known as quite unreactive dienophiles under usual Diels-Alder reaction conditions. We have examined our catalyst system, based on low valent cobalt phosphine complexes to promote the reaction of dialkoxyethynylboronates with various dienes. The reactions proceed under mild conditions and led to the dihydroaromatic boronic esters. / CoBr2dppe, Znl2 Ph = B(Oi-Pr)2 + /7—L * x '' \ Bu4NBH4orZn dust Ph B(Oi-Pr)2 Dihydroaromatic boronic esters were successfully used in the Suzuki cross-coupling reaction (with Hal-sp2, Hal-sp' systems) to prepare a wide range of 1,4-cyclohexadienyl substituted aromatic, heteroaromatic and unsaturated compounds, that could be easily oxidized by DDQ to give a variety of polysubstituted aromatic compounds. DDQ PdCI2dppf, NaOH. r^V^ R"Hal • L^ I - THF/H2O Ph""Y"^ benzene ph B(Oi-Pr)2 R" This sequence appeared to be very interesting and unusual retrosynthetic simplifications ot\ polysubstituted aromatic rings can be made. We also examined the possibility to use some boron containing 1.3-dienes [3] in the Co(I)-catalyzed neutral Diels-Alder reaction. The reaction of l-boronsubstinited 1.3-dienes generates 3-boronsubstituted-l,4-cyclohexadiene systems. Being bisallyboranes. chese compounds react with aldehydes to produce complex homoallylic alcohols, bearing tertiary and quaternary stereocenters with excellent diastereoselectivity. CoBr2dppe, Znl2 ^IiY" PhCHO TMS- Bu4NBH4 TMS de > 99% A chiral version of this neutral Dieis-Alder reaction is currently under investigation. 1. Matteson D. A.. Waldbillig J. O.,J. Org. Client. 1963, 28, 366. 2. Singleton, D. A.. Leung, s". W../. Org. Chem. 1992, 57, 4796. 3. Kamabuchi, A., Miyaura, N., Suzuki, A. Tetrahedron Lett. 1993, 34, 4827; Vaultier, M., Truchct, P., Carboni, B., Hoffmann, R. W., Dcnne, I. Tetrahedron Lett. 1987, 28,4X69. 149 P"72 RU0410130 THE REQUIREMENTS AND DEVELOPMENT OF BORON COMPOUNDS FOR NEUTRON CAPTURE THERAPY OF CANCER Albert H. Soloway8. Werner Tjarks'1 and Rolf F. Barthb a College of Pharmacy of The Ohio State University, e-mail: [email protected], tjarks.l(a;osu.edu; b College of Medicine and Public Health of The Ohio State University, e- mail: [email protected] The clinical use of Boron Neutron Capture Therapy (BNCT) for treating cancer has not been very successful to date. The question is why not? DNA repair within tumor cells from high linear energy transfer (LET) particles, such as lithium and alpha particles, does not occur. 10 n 7 4 ;B + on' -> [ 5B ]-> 3Li - :He + y 0.48 Mev + 2.31 Mev (94%) With concentrations of 20-35ug l0B,g and thermal neutron fluences of 1012—1013 a'cm2, destruction of tumor cells should result. But even at those levels, clinical results have been disappointing. The reason is that tumor cells with inadequate inB levels are not destroyed, and survivors become the basis for tumor recurrences. In measuring average tumor concentrations, some cells have greater amounts of'"B than required and others have inadequate levels. For the destruction of all tumor cells, the boron content needed is 104 IOB atoms cell. The results, even with appropriate neutron fluences, are disappointing. Therapeutic failure cannot be attributed to a paucity of boron compounds [1]. However, the cellular concentration of inB is very significant when compared with the chemical dosages of radiopharmaceuticals used in diagnosis. For a 70 kg person, the range is 0.1 - 8.4 ng, whereas for BNCT compounds the range is 1.4-2.4 g of 10B, a difference of nine orders of magnitude. Finally, in diagnosis not every tumor cell is targeted but in therapy each must be. It is unlikely for a single compound to penetrate all tumor cell membranes in a heterogeneous cellular mixture and achieve the necessary intracellular levels of 20-35 ug KIB/g. As in cancer chemotherapy, multiple agents are needed to attain the required boron content. Also, BNCT may be just one component in a multiple treatment regimen, i.e. in concert with other types of radiation and drugs. BNCT failure has been in not recognizing that the tumor is not monolithic but a diverse group of cells and the targeting focus must be at the cellular level. By focusing only on tumor tissue content itself, the approach has been simplistic. Recognizing that fact may determine which boron compounds are to be evaluated in cell culture and animals and what combination of agents is to be screened to mirror their clinical use. !. A.H. Soloway. W. Tjarks, B.A. Barnum, F.G. Rong, R.F. Barth, I.M. Codogni, J.G. Wilson. The chemistry of neutron capture therapy, Chcm. Rev. 98 (1998) 1515-1562. 150 P-73 RU0410131 Na8[FephthaIocyanine(CH2NH2Bi2H|,)8] FOR PDT AND BNCT R.A. Spryshkova ', R.G.Nikitina 2, E.Yu.Grigorieva ', V.I.Riabkova ! N.N.Blokchin Russian Cancer Research Centre, Moskow, Russia ' Medical Radiology Research Centre, Kaluga region, Obninsk, Russia At present some porphyrines and phthalocyanines are used for PDT. With the other hand it is supposed that these compounds (as they were found in tumours) can be useful for BNCT as means of delivery boron into tumours. In this work the possibility of using Nas[FePc(CH2NH2Bi2Hn)8] (I) for PDT and BNCT was studied. Pc= phthalocyanine, C^H^NgNaslTePctCH-^NI^B^Hn^] was synthesized in acad. N.T.Kuznetsov' laboratory, Institute of common and inorganic chemistry ofRAS. It was shown that in 3 hours after i.p. injection of I (50 ug B/g of body mass) into mice bearing s.c. B-16 melanoma the optimum conditions for BNCT were attained: the average boron content in tumours achieved 29.2 fig/g. At the same time boron level in the skin, blood and muscle was 4.7, 3.6 and 12.5 times lesser, accordingly. When PDT for rat sarcoma M-l was carried out it was shown that the best result of tumour growth suppression was got in 3 hours after i.p. injection of I as well: thus in 2! days after tumours irradiation (red light, 670 run) the factor of absolute tumour increase was the least and maked up 13.2±4. According to the data of this work Na8[FePc(CH2NH:B1:H|1)8] is suitable for PDT and BNCT and their combine application. 151 P-74 RU0410132 2 EXHAUSTIVE IODINATION OF B12H,: ~ AND ITS DERIVATIVES Victor A. Brattsev, Pavel A. Storozhenko and Ella L. Gourkova GM/ChTEOS, 38 Shosse Enhiziastov, 111123 Moscow. Russia, e-mail: eos(ipeos.incotrade.ru X-ray diagnostic agents usually used for medical studies of soft tissue diseases are usually based on different derivatives (mainly amides) of 2.3,5-triiodobenzoic acid, where iodine - X- ra\ contrasting element - is firmly bound in the molecule and not easily splitted off in the hu- man bod\. B-I-bond in iodinated icosahedral dianion B12Hj2~~ and carboranes is extremely stabic. apparently even more stable, than organic aromatic C-I-bond, that gives prospects for using functional derivatives of such iodinated species as new agents for X-ray diagnostics. The dianion B;2H;2~' (I) can be exhaustively halogenated to B]2Hali2~~ with Cl2, Br; and even I2 [1]. but for iodination a multihour heating is required, and rather often the reaction is not complete. An efficient method for the exhaustive iodination of I and its derivatives has been devel- oped. It consists in interaction of the B|2-substrate with excess of iodine and KICK according to the equation: : 2 2 5B12Hi2 - 24 12 - 12 KV + H2SO4 *• 5 B,2Ii2 ~ + 6 SO4 ~ + 36 H2O The reaction proceeds in aqueous sulphuric acid at room temperature, but in order to complete it the reaction mixture is refluxed for 1 hour. Earlier this reaction was successfully used for iodination of a- and ///-carboranes in water-soluble media [2]. As substituted B|2-derivatives 2 2 B|2H,,SCN " (H), 1.7-Bi2H1(1(SCN)2 " (III) and BI2H,|SC(NH2)2~ (IV) have been studied in the iodinations. It has been shown that anions II and III are fully iodinated under the same conditions: 2 + 2 B|2H,,SCN ' + I2 + IO3 + H • B12I11SCN ' The fully iodinatcd anions of II and III have been isolated as triethylammonium salts and characterized by nB NMR and IR spectra that confirm their structure, retention of SCN- groups and exhaustive iodination. The anion IV together with iodination undergoes oxidation of SC(NH2)2-group apparently into SChH. The forming Bi2I)]SO3FT~ is not precipitated from aqueous solutions as alkylammonium salts due to their high solubility. 1. W.Knoth, H.Miller, J.Sauer, et a!., Inorg. Chem. 3, 159-167 (1964). 2. V.Stanko, V.Brattsev, T.Vostrikova, G.Danilova, Zh. Obshch. Khim.,38, 1348 (1968). 152 P-75 RU0410133 BORON COMPOUNDS TECHNOLOGY E. Zheludov, B. Selyakov, O, Suchkova, M. Ulyantscv, V. Soldatov Dzerzhinsk Experimental Plant of Aviation Materials A VIABOR JSC, e-mail: [email protected] AVIABOR JSC is one of the leading world manufacturers of a wide range of boron compounds. For over ten years our company has been exporting over 90% of the whole production volume to countries of Europe, Asia and the USA. Our stock list comprises over 40 products including such items as Boron Trichloride, Diborane, Triethylborane which are a basis for obtaining a series of boron compounds. Manufacturing processes developed at the plant are unique and their onliness is based on specific properties of boron compounds. Many of the manufactured products have a high reactivity: they are hydrolyzed and oxidized in the air, thermally unstable and corrosive to materials and media. This condition requires a special approach to development of the relevant manufacturing process. Boron compounds having applications in electronic and pharmaceutical industry, as well as in medicine, their quality requirements are extremely high. Specifications of the boron compounds we produce excel those of the best foreign-made counterparts and are conditioned by the nature of synthesis as well as the use of high purity reagents. The plant research laboratory has the necessary sci-tech footing which allows to lead independent research projects protected by patents and custom-synthesize virtually any boron compounds. 153 P-76 "RU0410134 MOLECULAR HYPERPOLARIZABILITY OF NH:-NO2-SLBSTITUTED 6- AND 10-VERTEX CARBORANES. Kyrill. Yu. Suponitsky*, Tatiana V. Timofeeva, Michail Yu. Antipin A.N. Nesmevanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, Russia, e-mail: [email protected] Noniinear optical (Ts'LO) properties of organic compounds are the subject of the extensive investigation over the past decades due to their high NLO-efficiency in comparison to well- known inorganic materials. Hyperpoiarizability of planar push-pull conjugated molecules is well studied while less attention has been paid to carboranes - three-dimensional analogues of benzene. Investigation of carboranes as potential NLO materials is encouraged by their unusual thermal stability, which is significant for further applications. In the present study, peculiarities of the molecular structure and NLO responses of a series of NH^-NO^-substituted 6- and 10-vertex carboranes were theoretically investigated. Molecular geometries were fully optimized by density functional method (B3LYP) at the 6- 31-G* basis set. Estimation of the molecular hyperpolarizabilities was carried out in terms of finite field theory at static limit. The same level of sophistication was utilized. The results obtained have reveiled that NLO-efficiency of carboranes under study is 3 2 higher than that of/wra-nitroaniline (PV-NH2-C2B4H4-NO2= 37 (C-m) -r , P/,-NH2<-2B8H8-NO2= 22 := (C-m)"'-J"~, P/J_KH,-C-6H4-NO2 21 (C-raj^r). It allows us to consider push-pull carboranes as a promising class of compounds for nonlinear optics, taking into account their thermal stability. (54 P-77 RU0410135 ELECTRONIC EFFECTS OF CARBORANES IN THE SOLVOLYSIS OF (CARBORANYL)BENZYL TOSYLATES Yoshiyuki Taoda.a Takehiko Sawabe,a and Yasuyuki Endob a Graduate School of Pharmaceutical Sciences, The University oj'Toky-o, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan Tohoku Pharmaceutical University, 4-4-1, Komatsushima, Aoba-ku, Sendai 981-8558, Japan, e-mail: [email protected] Icosahedral carboranes are strongly electron-withdrawing groups, similar to halogen atoms. The order of the inductive effect of carboranyl moiety is ortho»meta>para-\somevs. In order to evaluate the detailed electronic effects of carboranes, we performed the solvolitic experiments of (carboranyl)benzyl tosylates. The rate of the acetolysis were consistent with the order of the inductive effect of carboranes. However, the hydrolysis of (o-carboranyl)benzyl tosylate (1) in aqueous dioxane was significantly accerated compared with those of other isomers m- (2) and /?-carborane (3). The measurements of the activation parameters revealed that only the hydrolysis of (1) has a large negative AS* value (ca -28 eu). Moreover, only the hydrolysis of optically active 1 gave the 70% retentive product, whereas the products from (2) and (3) were racemic. [1,2] Then, we examined the substituent effect on phenyl group of (carboranyl)benzyl tosylate. The hydrolysis of m-carboranyl derivatives (2) followed a Hammett correlation with p~ = -5.02. In contrast, the hydrolysis rate of theo-carboranyl derivatives (1) were almost constant in a rage of electron-releasing and electron-withdraving substituents (cf > -0.31). In regard to the characteristic solvolysis of (o-carboranyl)benzyl tosylate. we propose the two sets of SN2 mechanism involving the interaction of the nucleophiles and boron atom in the carboran caee. OTs OTs OTs 1. Endo, Y.; Sawabe, T.; Taoda, Y.J Am. Chem. Soc, 2000. 122, 180-181 2. Endo, Y; Taoda, Y. Tetrahedron Lett., 2001. 42, 6327-6331 155 P-78 RU0410136 NOVEL BROMO DERIVATIVES OF S.V. Timofeev, I.A. Lobanova, P.V. Petrovskii, Z.A. Starikova, V.I. Bregadze A. N. Nesmcyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova str., 119991, Moscow, Russian Federation, e- mail: [email protected] We have found that bromine readily reacts with exo-m'Jo-ruthenacarborane 5.6.10-(,p-Hr.-10-H-7.8-C2BuHx (1) giving complex 2 in which the chlorine atom is substituted for bromine in octahedral coordination sphere of ruthenium. H / H o PPh5 H-_.^_-^D-~# pph. ,n IPPII CIR H c -'-' "^H Jo - °o cn2<.-h \ A-^> \y \ / ^' H O'' H & o e_ni O-BH 1 O-B 2a 2b Bromination of the carborane cage does not proceed. Change of bromine to NaBr leeds to the same result but the yield of 2 significant increases. Structure of trans-isomcv 2a was established by single crystal X-ray diffraction analysis. Selected interatomic distances (A): Ru(l)...P(l) 2.3100(7), Ru(l)...P(2) 2.3060(7), Ru(l)...H(5B) 1.96(3), Ru(l)...H(6B) 1.94(3), Ru(l)...H(10B) 1.73(3), Ru(l)...Br(l) 2.5338(4); selected bond angles(°): P(2)- Rud)-Br(l)...96.89(2), P(l)-Ru(l)-Br(l)...95.77(2), Br(l)-Ru(l)-H(5B)... 85.3(8), Br(l)-Ru(l)- IK6B)...89.1(9), Br(l)-Ru(l)-H(10B)...175.5(11), P(2)-Ru(l)-P(l)... 100.67(3). Interaction of mercuro-derivative of the exo-«/Jo-ruthenacarborane, 10,10'-Hg-{exo- /;/Wo-5,6,10-[Cl(Ph3P)2Ru]-5,6,10-(y-H)3-7,8-C2B9HgJ2 (3) [1], with a sodium bromide was also investigated. The reaction leads to change of chlorine atoms to bromines giving A mixture of trans-(4a) and c7.v-(4b)-isomers which were separated by column chromatography. This work was supported by Russian Foundation for Basic Research (grants 02-03-32192 and 00-03-32807). 1. I.A.Lobanova, V.l.Bregad/.e. S.V.Timofeev, P.V.Petrovskii, Z.A.Starikova, and i .M.Dolgushin, J Organomel. Chem. 2000,597,48-53. 156 P-79 RU0410137 1,1-VINYLBORATION OF ACETYLEMC DERIVATIVES OF SILICON AND TIN Oleg L. Tok, Bernd Wrackmeyer Laboratorium Jiir Anorganische Chemie der Universitdt Bayreuth, D-95440, Germany [email protected], [email protected] The organoboration of acetylene derivatives of silicon and tin with trivinylborane (1) was investigated for the first time and the results will be discussed. The presence of unsaturated fragment near boron atom makes the organoboration reaction more complicated compared with "normal" triorganoboranes (i.e. triethylborane). Thus, the reaction of I with the monoacetylenic derivatives of silicon and tin gives the mixtures of l,2-ra-/?ra^y-boronmetalsubstituted defines. When the starting acetylenes contained bulky substituents (such as M^Si, Me^Sn or z-Bu) the corresponding allenes were formed qualitatively. 1,1-Vinylboration leads to the formation of 2-(R:B)-buta-l,3-diene with boron-containing substituent in allylic position which can easily migrate by sigmatropic [1,3]B shift to the terminal carbon atom to give of 4-(R:B)-buta-l,2-diene system. R = Me3M. f'Bu X = Me Me2XM- M = SiorSn MXMe, \ 2B R - =! R =^ MXMe2 R = Me, Bu X = Me, H With more than one eqvivalent of an acetylene compound all three vinyl groups can take part in 1,1-organoboration reaction independently to give mono-, bis- and tris(homoallenyl)boranes. At the ratio 1:3 the symmetric triorganoboranes were obtained almost quantativcly. 157 P-80 RU0410138 POSSIBILITY OF SUPERCONDUCTIVITY AT 110 K IN INCLUSIONS OF PHASES IN DIFFUSE BORIDE LAYERS ON TITANIUM V. V. Volkov , K.G. Myakishev , P. P. Bezverkhy , V. G. Martynets , E. V. Matizen Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Novosibirsk 630090, Russia, e-mail: [email protected] Theoretical predictions have been published claiming that a new row of high-temperature su- perconducting (HTSC) systems is possible on the basis of titanium borides. A theoretical phase diagram was published [1] that depicts the region of the compositions of boride phases TiBk for which HTSC is possible (Fig. 1). namely, for 1.43 composite materials at Tt. The diffuse boride layers were deposited onto Ti - metal by treating titanium samples with a mixture BiHfXgj+H: at 610- 700 C, followed by annealing in vacuum. R/Ro b - 1, cooling R/R^ 0,9 0,9 2, cooling • 3. cooling 3, heating -v. 0,8 ** 1 • 0,8 T, K 07 50 100 150 200 250 Fig. I. Phase diagram of TiB],. The HTSC areas are shaded. Here: np - number of p-vacant electron sites in 2p4 - shell of B - anions, n,j - the same in 3d4 - shell of Ti - cations. The clectroneutrality lines of some TiB^ are showed by straight dashed lines. Fig 2. Dependencies of' R (Tj/Ro for samples I (a), 2 and 3 (b). !. Zaitsev R.O. Superconductivity: phys. chem. engin. 2, .N«12, 36-40 (1989), in Russian. 2. Volkov V.V., K.G. Myakishev , P. P. Bezverkhy , V. G. Martynets , E. V. Matizen.Inves- tigated in Russia. http://zhurnal.ape.reiarn.ru/articles/2002/045.pdf (in Russian), http:/;zhurnal.ape.relarn.ru/articles/2002/045c.pdf (in English). 158 P-81 RU0410139 RADIOLABELLING OF IODINATEDO, m AND/J-CARBORANES USING PALLADIUM CATALYSED ISOTOPIC EXCHANGE Karl Johan Winbcrg1, Ludvig Eriksson1, Vladimir Tolmachcv2, Gemma E3arbera\ Clara Vifias3, Francesc Teixidor3 and Stefan Sjoberg1 * Department of Organic Chemistry, Institute of Chemistry, Uppsala University, P.O. Box 531, S-751 21 Uppsala, Sweden, e-mail*: [email protected];" Division of Biomedical Radiation Sciences, Box 535, S-751 21, Uppsala University, Uppsala, Sweden:' Institut de Ciencia de Materials de Barcelona, C.S.I.C., Campus U.A.B., 08193 Bellaterra, Spain We have previously successfully labelled /?-carborane in the 2-B-position with ~ I using palladium catalysed isotopic exchange [1]. We have now extended this work to include the labelling of some other c/oso-carboranes. Thus, the labelling of 3-iodo-o- [2], 9-iodo-o- and 9-iodo-m-carborane proceeded cleanly in 90-95 % labelling yield within 10 minutes. High yield were also obtained in the radioiodination of some recently reported [3] iodinated C-substituted o-carborane by derivatives. In the Scheme below, the palladium catalysed radiolabel ling of 3-iodo-c/avo-carborane using isotopic exchange is illustrated 125i 125I", Pd-cat, N^* O = CH n =B/BH We are indebted to the Swedish Cancer Foundation, [NTAS (grant 99-00806), the Royal Swedish Academy of Science and CICYT (Project MATOl-1575), Generalitat de Catalunya (2001/SGR/00337) for financially support of this project. 1. L. Eriksson, V. Tolmachev and S. Sjoberg. Submitted. 2. J. Li, C. F. Logan and M. Jones Jr. Inorg. Chem. 1991, 30, 4866. 3. C. Vinas, G. Barbera, J. Oliva, F. Teixidor, A. J. Welch and G. M. Rosair Inorg. Chem. 2001, ¥0,6555 150 P-82 RU0410140 SYNTHESIS OF BORONIC ACIDS AND BORONATED AMINO ACIDS IN IONIC LIQUIDS Andrzej Wolan and Marek Zaidiewicz Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland, e-mail: [email protected]; [email protected] Ionic liquids are promising new solvents of high potential for organic synthesis. Unique properties, such as negligible vapour pressure, high thermal stability, easy handling, and the ability to dissolve both inorganic and organic compounds contribute to their increasing applications. Recenth. ionic liquids based on 1.3-dialkylimidazolium cations were used as reaction media for hydrogenations, Suzuki cross-coupling, Heck and other reactions [1,2]. Arylboronates can be prepared by the classical transmetalation methodology from aryl magnesium or lithium reagents and alkylborates. Alternatively, the palladium-catalysed cross- coupling of aryl halides with tetraalkoxydiborons or the more readily available pinacolborane can be employed. Herein we report the coupling of pinacolborane and 5.5-dimethyl-[l,3,2]dioxaborinane with aryl halides in the following ionic liquids [emimJfBF}]. [emiin][PFc], [bmim][BF4], [bmim][PF,]. [hmim][BF4]. [hmim][PFft], [bpy][BF4] and [bpy][PF6]. O~-x R / \ 3 % mol PdCI2(dppf) + H—B 1 ' \ J ionic liquid 0 3equiv. Et3N, 100 °C X - I, Br 70 - 89 % The coupling reaction of dialkoxyboranes with aryl iodide and bromide in the presence of base and a catalytic amount of PdCbi'dppf) carried in ionic liquids provided the corresponding arylboronates in high yields. Generally, aryl iodides exhibited higher reactivity than aryl bromides [3]. The ionic solvent allows to complete the reaction in a short time without decomposition of the palladium catalyst, and facilities the product isolation. The ionic solution containing the catalyst can be reused without loss of the catalytic activity. A significant acceleration of the reaction in the ionic liquid was observed for the protected /;-iodophenylalanine, which reacted in 20 min producing the coupling product in 89 % yield. 1. P. Wassersheid, W. Keim, Angew. Chem. Int. Ed., 2000, 39,3112. 2. T. Welton. Chcm. Rev., 1999, 99, 2071. 3. M. Zaidiewicz. A. Wolan,./. Or^anomet. Chem., 2002, in press. 160 P-83 RU0410141 UTILITY OF BORON CLUSTERS FOR DRUG DESIGN: HYDROPHOBICITY OF CARBORANES Keisuke Yamamoto,a and Yasuyuki Endo a Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan Tohoku Pharmaceutical University, 4-4-1, Komatsushima, Aoba-ku, Sendai 981-8558, Japan, e-mail: [email protected] Dicarba-c/o.vo-dodecaboranes (carboranes) are chemical building blocks of high boron content. remarkable thermal and chemical stability, spherical geometry and exceptional hydrophobic character. Their unusual properties make them uniquely suitable for several specialized applications in the field of materials sciences and biomedical sciences. We previously reported carborane moiety is potent hydrophobic pharmacophore in the structures of several nuclear receptor ligands [1], while the quantitative hydrophobic character of carboranes is unknown. In order to evaluate the hydrophobicity of carboranes, we analyzed the water/1-octanol partition coefficients (log P) of various 4-carboranylphenol by HPLC method [2]. We synthesized eight isomeric 4-carboranylphenols (1 - 8), depending on three rsomeric carboranes (ortho, meta, and para) and the position of carboranes attached to the phenol moiet\ as shown below. Interestingly, log P of 1 - 8 varied in wide range (4.11 - 5.86). 4-(/?-Carboran-l-yl)phenol (1, log P = 5.86) is most hydrophobic, and more hydrophobic than 4-(l-adamantyl)phenol (log P = 5.46). 4-(o-Carboran-9-yl)phenol (8, log P = 4.11) is least hydrophobic, and less than 4-cyclohexylphenol (log P = 4.40). The detailed procedure and structrure-hydrophobicity relationship will be discussed. H OH OH H H 1. Endo, Y; lijima, T; Yamakoshi, Y, Fukasawa, H.; Miyaura, C; Inada, M.; Kubo, A.; Itai, A, Chemistry and Biology, 2001, 8, 341-355. 2. Yamamoto, K.; Endo, Y. BioMed. Chem. Lett. 2001, 11, 2389-2392. 161 P-84 inn RU0410142 A CATALYTIC CYCLE INVOLVING RHODIUM-X INYLIDENE COMPLEX FOR FORMAL r/?^A5-HYDROBORATION OF TERMINAL ALKYNES Kenji Yamaguchi, Toshimichi Ohmura, Yasunori Yamamoto, and Norio Miyaura Division of Molecular Chemistiy, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan, e-mail: miyaiira@,org-mc.eng.hokudai.ac.jp We recently reported that the rhodium(I)-triisopropylphosphine complex catalyzes the formal //Ym.v-hydroboration of terminal alkynes with catecholborane [1]. The reaction provides a convenient method for the synthesis of (Z)-alkenylboron compounds from the representative terminal alkynes. The mechanistic study suggested diat the reaction involve the formation of a vinylidene complex as the key intermediate because the deuterium labeled at the terminal carbon of alkynes selectively migrated to the p-carbon of the products (Eq. 1). 1. [Rh(cod)Cll2-4P(/-Pr)3 D Et3N, cyclohexane » n-C6H13—=—D + H-B( J\ 1 '• • n-C6Hi3 Bpin (1) O*"*^^ 2. pinacol (>96% d,) 75o/o The NMR study of the intermediates indicated a catalytic cycle shown in Figure 1. The oxidative addition of an alkyne is followed by its conversion into a vinylidene complex. This process was significantly accelerated in the presence of EtjN. Although the vinylidene complex is highly inert to the borane reagent, we found that one phosphine ligand is easily displaced by an alkyne to give an alkyne-rhodium complex which allows addition of a borane-amine complex. The addition from the opposite side of the substituent (R) yields aZ-alkenylrhodium intermediate for the reductive elimination of aZ-alkenylboron product. 1. Ohmura, T; Yamamoto, Y.; Miyaura. N.J. Am. Chem. Soc, 2000, 122, 4990. 162 P-85 RU0410143 THE REDUCTION OF CUBANE DERIVATIVES WITH VARIOUS FUNCTIONAL GROUPS BY SODIUM BOROHYDRIDE IN DIFFERENT SOLVENTS V.V. Zakharov, G.P.Bugaeva, V.S.Malygina, L.B.Romanova and L.T.Eremenko Institute of Problems of Chemical Physics, Russian Academy of Science, Chernogolovka, Moscow Region, 142432 Russia, t-mail: vzakh(i.v,icp.ac.ni In the connection with sharply increasing interest in cubane derivatives as potential phannaceutic preparations [1], and multistage character of their synthesis the development of effective selective methods for modifying compounds with a cubane structure is very actual. In the present paper the reduction of 4-methoxycarbonylcubanecarboxylic acid monochloride (1) and 4- methoxycarbonylcubanecarboxylic acid (2) with sodium borohydride in different solvents (dioxane, water, dioxane-THF). The reduction of 1 sodium borohydride in dioxane at low temperature was shown to give together with l-hydroxymethyl-4-methoxycarbonylcubane (3) also 1,4- bis(hydroxymethyl)cubane (4). The effective method for preparing 3 was developed by the following reaction: CCXX'Hi CUX'H.! -lOtnn. 0-5"C vie Id 7U° o COC1 en' 1 By the reduction of 2 with sodium borohydride 4-hydroxymethylcubanecarboxylic acid (5) was prepared for the first time and identified with the 1R. 'H and ''C NMR spectra. elemental analysis. COOH COOK 2 h, 2O-25°C vield 85-87°0 COOCIb CH-O11 2 5 The authors wish to thank G.V.Lagodzinskaya and V.P.Lodygina for the analysis of the !H- and "C-NMR, IR spectra. This study was financially supported by the International Science and Technology Center (Project No 1550). 1. L.T.Eremenko, L.B.Romanova, M.E.Ivanova. D.A.Nesterenko, V.S.Malygina, A.B.Eremeev, G.V.Lagodzinskaya, and V.P.Lodygina, Russ. Chcm. Bull., 1998,47, 1137- 1140. 163 P-86 RU0410144 NUCLEOPHILIC SUBSTITUTION IN CLOSO-DECABORATE ANION K.Zhizhin, V.Mustyatsa, I.Polyakova, L.Goeva, N.Kuznetsov Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science Leninisky pr., 31, Moscow GSP-1, 119991 Russia, e-mail: [email protected] Interaction between the closo-decaborate anion and the carboxylic acids is studied. The mono-, 2 di-. tn-. and tetrasubstituted products BioHi(Mi(OCOR)n " (n = 1-4, R = H, CH3, C2H5, C3H7, C4H9) are formed step-by-step on heating. The reaction proceeds by the regioselective mechanism and results in the formation of only one of all the possible isomers at each stage of the process. Alkaline hydrolysis of these products in aqueous and nonaqueous solutions affords the BjoHio n(OH),r hydroxy-closo-decaborates. It is suggested that the process of substitution of the carboxylate groups for the exo- polyhedral hydrogen atoms in BIOHKT" includes the following stages: (1) formation of the associate upon the dissolution of a decaborate salt in the acid; (2) elimination of the acid residue and formation of the intermediate BHJHH" anion; and (3) detachment of H2 on heating and directed nucleophilic attack on the vacant equatorial site. 2 2 Mixed-ligand lead(II) complexes with the BIQHHM^OCOR),, " or BioHiu_n(OH)n " polyhedral anion and 2.2'-bipyridyl are synthesized and characterized by IR spectra and X-ray diffraction. C(9) ,CI8I [Pb(bipy)(B,()Hy(OC(O)CH3))2f [Pb(bipy)2BluHx(OC(O)CH3)2]. 164 P-87 II li RU0410145 PRENYLBORATION OF 3-R-INDOLES Yu. N. Bubnov, A. V. Ignatenko, 1. V. Zhun1 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, GSP-1, Leninsky prosp., 47, Moscow, Russia. E-mail [email protected] 3-R-Indoles undergo reductive 1,2-isoprenylboration upon treatment with tri(3-methylbut-2- enyl)borane (triprenylborane) to give after deboronation the corresponding trans-2- isoprenylated-3-R-indolines in a yield 80-90%. 1,2-Addition occurs with full rearrangement of allylic moiety [1]. We use this reaction as a key step in first total synthesis of debrominated analogue of alkaloid Flustrabromine produced by marine bryozoan Flustra Foliacea [2]. NHMe NHMe ~COOH 3 steps i 73% H 3, 93% HCO2Et. NMeCHO 90-100°C, 1 h . NMeCHO NMeCHO ^p-Chlorany[ Flustrabromine, I isolated from Flustra Foliacea H ' ' 5, 50% 4, 73% (baltic marine bryozoan) Debromoflustrabromme Transformation of indole 2 to the product 3 proceeds on heating and completed in 4.5 h. Further protection of the amino group with ethyl fomiiate and aromatization of 4 obtained by/7-chloranyl gives debromoflustrabromine. The work was supported by Russian Foundation for Basic Researches (grants .Ve 99- 03-33l25a and 00-15-97378) and program "The Integration" (grant.\r9 234). 1. Yu. N. Bubnov, I. V. Zhun, E. V. Klimkina, A. V. Ignatenko, Z. A. Starikova, Eur. J. Org. Chem. 2000, 3323-7. 2. J. S. Carle, C. Christophersen, J. Org. Chem. 46, 3440-3 (1981). 165 IMEBORON XI - List of Contributing Authors IA/IB = Invited Lecture CA/CB = Contributed Lecture P = Poster Session Ali Hijazi Abu P-18 Glazun S.A. P-12 Backovsky Jaroslav P-l Gorshkov Alexander P-13 Bakardjiev Mario P-2 Greatrex Robert CA-1 Barba Victor P-3 Gribanova Tatyana P-14 Barton Lawrence IA-10, P-4 Gridnev Ilya CB-1 Batsanov Andrei P-5 Grimes Russell N. IA-8 Beckett Michael A. CB-10 Griiner Bohumir CA-6 Bemdt Armin 1B-7 Gul'malieva Maya P-15 Bochmann Manfred IB-8 Gurskii Mikhail P-16 Bragin Vikentii P-6 Haubold Wolfgang P-17 Brattscv Victor CB-5 Hawthorne M. Frederick IA-1 Brcllochs Bernd CA-8 Hey-Hawkins Evamarie CB-13 Cheredilin Dmitrii N. P-7 Hnyk Drahomir P-19 Chizhevsky Igor T. CA-9 Holub Josef P-20 Do Youngkyu CA-12 Hosmane Narayan S. IA-5 Einholz Wolfgang P-8 Ikorskii Vladimir P-21 Endo Yasuyuki IB-9 Janousek Zbynek P-22 Eriksson Ludvig P-9 Jelinek Tomas CA-2 Eilin A.M. P-10 Kabalka George W7. 1B-3, P-23 Franken Andreas CB-7 P-24, P-25 (label Detlef 1B-12 Kagechika Hiroyuki P-26 (ievorgyan Vladimir CB-2 Kakizawa Taeko P-2 7 (ihirmai Senait P-l 1 Kalinin Valery IB-1 166 Kang Sang Ook IA-13 Ol'shevskaya Valentina CB-X Karionova Anna P-28 Paavola Sari P-57 Kaszynski Piotr CB-12, P-29 Paetzold Peter IA-I 1 P-30 Pcrekalin Dmitry S. P-5S Kaufman Dieter E. IB-11 Pershin Dmitrii CB-14 Kavvano Yasuro CA-7 Polyanskaya Tamara p_59, p-6() Keller Willi P-31 Ponomarev Vladimir CB-4 Kennedy John IA-4 Prewysz-Kwinto Andrzej P-61 Khokhlov Vyatcheslav F. P-32 Quntar Abel Al Aziz P-62 Kitaev Peter P-33 Ramachandran P.V. IB-6 Kizas Olga P-34 Renard Edouard V. P-63 Kodess Mikhail I. P-35 Rozenberg A.S. P-64 Kononova Elena P-36 Safronov Alexander V. CA-5 Konoplev Vitalii E. P-37 Scherban Vyacheslav P-65 Koryakin Sergey P-38 Semioshkin A.A. CB-15 Kosinova Marina P-39 Shelkovnikov Vladimir P-66 Koulakov Victor P-40 Shimoi Mamoru CA-3 Krasnov Victor P-41 Shirokii Valerii P-67, P-6S Krzeminski Marek P-42 Siebert Walter IA-3 Kudinov Alexander CA-4 Singh Vijay Pal CB-16. P-69 Kuznetsov Nikolai T. P-43 Sivaev Igor CA-15 Kuznetsov V.V. p-46, P-47 Sjciberg Stefan CB-6 Kuznetsov Nikolai Yu. P-44, P-45 Skachkov Alexander P-70 Loginov Dmitry P-48 Smolko Konstantin P-71 Londesborough Michael CA-16 Sneddon Larry IA-12 Makhaev Victor P-49 Solo way Albert P-72 Malinina Elena P-50 Spryshkova Raisa P-73 Maltseva Nina P-51 Stibr Bohumil IB-2 Matteson Donald S. IB-4 Storozhenko Pavel P-74 Meshcheryakov Vladimir P-52 Suchkova Olga P-75 Mikulasck Libor CA-14 Suponitsky Kyrill Yu. P-76 Minyaev Ruslan CB-9 Taoda Yoshiyuki P-77 Moiseev Sergei P-53 Teixidor Francesc IA-9 Muratov Dmitry V. P-54 Thornton-Pett Mark CA-10 Mustyatsa Valery P-55 Timofecv S.V. P-78 Nakamura Hiroyuki CB-3 Tok Olcg L. CB-11, P-79 Olejniczak Agnieszka P-56 Vespalec Radim CA-11 167 Vinas Clara CA-13 Yamamoto Yasunori P-84 Volkov Vladimir P-80 Yamamoto Keisuke P-83 Wade Ken IA-2 Zaidlewicz Marek IB-5 Welch Alan J. IA-6 Zakharov Viktor P-85 Winberg Karl Johan P-81 Zhizhin Konstantin P-86 Wolan Andrzej P-82 Zhun1 Ilya P-87 Xie Zuowei IA-7 Yamamoto Yoshinori 1B-10 168 Author Index Akula. M. R. 102 Bubnov, Yu. N. 34,68.93,94. 106. 107 Albrecht, K. 66 112. 122. 123, 165 Ali, Hijazi Abu 96. 140 Bugaeva. G. P. 163 Amseis, P. 48 Bukalov, S. S. 114 Antipin, M. Yu. 34,88, 154 Burke, A. 41 Antsyshkina, A. S. 127 Burmester, Chr. 66 Apeloig, Y. 66 Charushin, V. N. 113. 1 19 Asano, Toru 32 Cheredilin, D. N. 49.85 Ayupov, B. M. 117 Chizhevsky. I. T. 37,49.85, 115 Baca, J. 39 Chung, Minchul 62 Ba'kov; ky, J. 79 Chung, Seung-Won 75 Bakardjiev, M. 80,98 Chupakhin, O. N. 113. 119 Bakhmutova, E. V. 88 Cisa«ova, I. 39, 67, 98 Balagurova, E. V. 49.85 Cowan, J. A. 83 Balinski, A. 108 Cytarska. J. 36 Bao, Weiliang 103 Dalil. H. 90 Barakovskaya, I. G. 85 Danilova. G. X. 38 Barba, V. 81 Das. B. C. 101 Barbera, G. 63. 159 Davankov, V. A. 131 Barth. R. F. 150 de Vos. D. 90 Barton, L. 59,82 Do, Youngkyu 33 Batsanov. A. S. 83 Dolgovesova. I. P. 117 Bazhanov. A. V. 145. 146 Dolgushin. F. M. 37.49. 85. SS. 112. 115 Beckett, M. A. 54 Dorfler. U. 53. 74 Berndt, A. 48 Douglass. A. G. 108 Bezverkhy, P. P. 158 Dozol, J. F. 39 Biesemans, M. 90 Drozdova. M. K. 99. 137. 138. 144 Blaurock, S. 64 Dziele'dziak. A. 36 Bochmann, M. 52 Emhoiz. W. 86 Bollu, V. 103 Ellis. D. 41 Borisov, A. P. 127 El-Zaria, M. 74 Bould, J. 29.71 Endo, Yasuyuki 56, 104. 155. 161 Boyd, A. S. F. 41 Epstein, L. M. 88 Bragin, V. 84 Erdyakov, S. Yu. 106 Brattsev, V. A. 38, 116, 152 Eremenko. L. T. 163 Bregadze, V. I. 69,70,84,88,90. 118, Eriksson, L. 87, 159 156, Evstigneeva, R. P. 46.91 Brellochs, B. 45 Ezhikova, M. A. 113 Brown, J. M. 26 Fainer, N. I. 117 Brown, L. 53 Farfan, N. 81 Ferrer. D. 41 169 Film, A. M. 88 Hnyk, D. 97 Forsthocfel. K. M. 73 Hofmann, M. 23, 48 Fox. M. A. 21 Holub, J. 80.98, 100 Franker), A. 27 29.44.49 Hong. Eunkee 33 Fuentealba. P. 10? Hosmane, N. S. 35 Gabel. D. 74 Howard. J. A. K. 83 Geiderikh. A. V. 105 Ignatenko, A. V. 165 Ciciseler, G. 48 lkovskii. V. N. 99 Geuirgyan. V. 28 IFin. M. M. 131 Ghirmai. S. 89 Ionov. S. P. 121 Gielen. M. 90 lvanova. Z. I. 144 Giles. B.T. 41 Jang. Hyosook 33 Gliinzel. D. 86 Janousek. Z. 100 Glazun. S. A. 90 Jeli'nek. T. 27.29 Goda, Mio 32 Jeoung. Sae Chae 33 '(joeva. L. 1215. 164 Ju. Yuhong 24 Goldberg. I. 143 Jung. Byung Jun 33 Golmarkua. A. I. 12? Kabaika. G. W. 24, 101. 102. 103 Ciorshkov. A. Y. 91 Kagechika. Hiroyuki 104 (Ti Mi'koN a. E. L. 152 Kakizawa. Taeko 105 Greatrex. R. 25 Kalinin. V. N. 19. 113. 119, 131 Green. J. F. 101 Kang. Sang Ook 75 Greiwe. P. 23 Karionova. A. L. 68, 106 Gribanoxa. T. N. 50.92 Kaszynski. P. 62. 107, 108 Gridnev. I. D. 26 Kaufmann. D. E. 66 Gngorieva. E. Yu. 151 Kawachi. Emiko 104 Grimes. R. N. 51 Kawano. Yasuro 31,43, 105 Grintsele\-Knyazev. G. V. 61. 111. 130. 136 Keller. W. 95, 109 Grishakox. A. N. 119 Kennedy. J. D. 25,27.29,44,49,53,71 Gruner. B. 39.67 Khokl.lov. V. F. no, ii8 Guil'malieva. M. A. 4fi.93 Kilner, C. A. 29,44,71 Gurskii. M. E. 34,68.94, 106, 107 Kim. Sung-Joon 75 Man. Younggyu 33 Kitaev. P. S. 111 Han. Young-Kyu 33 Kivekas. R. 63, 135 Harvey, J. E. 1C8 Kizas, O. A. 112 I Fata. Mitsuhiro 59 Klimova, T. P. 118 Haubold. W. 95, 109 Ko. Jaejung 75 Hawthorne. M. F. 2C Kodess, M. I. 113 Ilcrberich. G. E. 132 Kolesov. B. A. 117 1 lev-Hawkins, li. 64 Kononova, E. G. 114 Hilt. G. 149 Konoplcv, V. E. 49, 115 i70 Korostylev. A. 26 Malygina. V. S. 163 Koryakin, S. 116 Marder. T. B. 83 Kosinova, M. L. 117 Markov, R. V. 144 Koster, M. 66 Martynets, V. G. 158 Koulakov, V. N. 110, 118 Mason, S. A. 83 Kozlovskaya, N. G. 110 Massa, W. 48 Krasnov, V. P. 113, 119 Matizen, E. V. 158 Krzemi'ski, M. 120 Matteson, D. S. 30 Kudinov, A. R. 61, 111, 126, 130, 132, Maulana. 1. 64 136, 143 Mavrinsky, D. N. 132 Kulikiewicz, K. K. 62, 108 Mclntosh, R. 41 Kulikov, P. V. 126 Mclntyre, G. J. 83 Kuznetsov, N. T. 121, 128, 129. 133, 164 McQuade. P. 59 Kuznetsov, N. Yu. 122, 123 Mesbah, W. 48 Kuznetsov, V. V. 124, 125 Meshcherikova, V, V. 110. 118 Kwiatkowski, M. 134 Meshcheryakov. V. I. 111,130 Laguna, M. A. 41 Meyer, F. 65 Lam. VV. H. 83 Mikulasek, L. 67 Lebedev, R. V. 131 Minyaev, R. M. 50.92 Lee. Young-Joo 75 Mitin, V. N. 110 Leites, L. A. 114 Miyaura, Chisato 56 Lesnikowski. Z. 134 Miyaura, Norio 162 Levit, G. L. 113, 119 Moiseev. S. K. 131 Lin. Z. 83 Morris, J. H. 38. 46 Lobanova. I. A. 156 Miiller, J. 65 Loginov. D. A. 126 Muratov. D. V. 126, 132 Lonime. P. 65 Mustyatsa. V. 133. 164 Londesborough. M. G. S. 29.71 Myakishev, K. G. 117. 158 Lonnecke. P. 64 Nakamura. Hiroyuki ?2 Lundqvist. H. 89 Namboodiri. V. 103 Luzgina. V. N. 46.91 Natarajan. N. 101 Lyssenko. K. \. 34.61. 114, 136 Nechiporenko. G. N. 142 Macgregor. S. A. 41 Nikishkin. N. 1. 146 Maier, A. 23 Nikitina, R. G. 151 Maier, C. J. 23 O'Dowd. C. 53 Maier, N. A. 145, 146 Ohmura, Toshimichi 162 Makhaev. V. D. 127 Olejniczak, A. 134 Maksiniovskii. E. A. 117 Ol'shevskaya, V. A. 19,46,91,93. 113. 114 Malinina. E. 128 119 Malmquist, J. 89 Orlova. N. A. 144 Maltscva, N. N. 129 Ormsby, D. L. 25,41 171 Paavola, S. 135 Sadikov, G. G. 127 Paetzold. P. 65 Safronov, A. V. 37 Pakhomov. S. 62, 107, 108 Sahin, Y. 48 Pangan, L. N. 31 Santillan, R. 81 Pastukhov. F. V. 93, 122 Satoh, F. 117 Pender, M. J. 73 Savin, A. 109 Perekalin. D. S. 61. 136 Savina, E. 116 Pershin, D. G. 34. 68, 94 Sawabe. Takehiko 155 Petrovskii. P. V. 37.46.61.90.91.93. Sawitzki. G. 95 111. 115. 126. 130. 132. Scherban. V. 143 136. 143. 156 Schmidt. F. 41 Piecek, W 108 Selucky. P. 39 Pisareva. I. Y. 49. 115 Selyakov. B. 153 Plekhanov. A. 1. 144 Semenuk, A. 134 Picsek. J. 39. 79 Semioshkin. A. 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