DOCSLIB.ORG

Tetrakis[Triorganylphosphineaurio(I

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Tetrakis[Triorganylphosphineaurio(I 1,1,1,1 -Tetrakis[triorganylphosphineaurio(I)]ethanium(+) Tetrafluoroborates - Hypercoordinated Species Containing [H3C-C(AuL)4I+ Cations Oliver Steigeimann, Peter Bissinger, and Hubert Schmidbaur* Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstraße 4, D-W-8046 Garching Z. Naturforsch. 48b, 72-78 (1993); received September 10, 1992 Auriophilicity, Gold(I) Phosphine Complexes, Ethane-tetraaurio(I) Compounds, X-Ray Hypercoordinate, tetraaurated carbon-complexes of the type [H 3C -C (A uP R 3)4]+BF4~, R = Ph (1), R = C6H u (2), (PR3)2 = l,2-C 6H4(CH 2CH 2PPh 2)2 (3) have been prepared by the reac­ tion of the appropriate (phosphane)gold(I) chlorides with l,l,l-tris(dimethoxyboryl)ethane H 3C -C [B(O M e)2]3 in the presence of CsF. The products have been characterized by standard analytical and spectroscopic methods, including single crystal X-ray analyses of 1 and 2. In each case the pentacoordinated carbon atoms have been located at the centre of a square pyr- amide built up by a methyl group at the apex and four gold atoms forming the base with short Au ••• Au distances of about 2.85 A, which strongly contribute to the formation and stability of these species. Introduction The special position of gold in the Periodic gation of complex units L -A u-X of phosphane Table is largely based on relativistic effects [1], gold compounds [3], but also to a clustering of which modify significantly the properties of the gold(I) atoms at or around a main group element valence electrons of Post-Lanthanide elements. like carbon, nitrogen, phosphorus, arsenic, oxy­ The relativistic contraction of the 6 s orbitals of the gen, sulfur, and selenium [4-10]. Apart from spe­ heavy elements reaches a pronounced local maxi­ cies with a more conventional stoichiometry mum for gold and leads to a break-up of the 5d 10 [(AuL)3E]+ (E = O [8], S [9a], Se [10a]), closed shell of electrons in the Au(I) oxidation [(AuL)4N]+ [5a-c,7], [(AuL)3NR]+ [5e-g], state. A wealth of evidence has been obtained from [(AuL)3PR ]+ [6], or C (A uL )4 [6c], novel cations structural and spectroscopic studies of both mono- [(AuL)4As]+ [7] with a nonclassical square-pyrami- and polynuclear gold(I) compounds for the exist­ dal structure and the unprecedented hypercoor­ ence of the resulting metal-metal bonding between dinated cations [(AuL) 5C]+ [4d], [(AuL)6C]2+ Au+ centers [2], Intra- and intermolecular metal- [4c, e-h], [(AuL) 5N]2+ [5d], and [(AuL) 5P]2+ [6 a] metal interactions give rise not only to the aggre­ have been discovered. r— — 2 + — _ n+ — L Au Au R 1 ..-A u L 1 ,,-A u L 1 LAu — X '' x LA u^ | "'^AuL | ^ * A u L LAu'"^ \^"'AuL Au Au LAu AuL L _ _ _ _ B: X = C, n = 1 E: X = C, n = 1 C: X = N, n = 2 F: X = P, n = 2 D: X = P, n = 2 * Reprint requests to Prof. Dr. H. Schmidbaur. While the number of homoleptic species A -D with the interstitial atom in the center of trigonal Verlag der Zeitschrift für Naturforschung, D-W-7400 Tübingen bipyramids or octahedra of gold atoms has been 0932-0776/93/0100-0072/$ 01.00/0 steadily increasing, only two examples are known Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. O. Steigeimann et al. • Tetraaurio(I) Complexes 73 to date where the coordination sphere around the from the reaction of 1,1, 1-trichloromethane and hypercoordinate central atom contains also a non­ ClB(OM e)2 with lithium powder in tetrahydro- gold substituent (E,F): These two dications furan, as described by Matteson et al. [11], the [RP(AuL)4]2+ [6 b] (R = o-tolyl) and (dimeric) analogous reaction led to the title compounds. The [RC(AuL)4]+ [4 b] (R = oxazolinyl) feature square gold(I) chloride complexes of PPh3, P(C 6H ,,)3 and pyramidal structures with, respectively, phospho­ l,2-C6H 4(CH 2CH 2PPh 2)2 required, were readily rus or carbon at the center, the R substituent at the available via published methods [ 12, 13, 4 e]. apex, and the four gold atoms at the base of the Treatment of the individual (phosphine)gold(I) polyhedron, with short Au-- Au contacts, indica­ chloride with l,l,l-tris(dimethoxyboryl)ethane in tive of the origin of this unusual clustering of gold the presence of cesium fluoride in hexamethyl- in both cases. phosphoric triamide (HMPT) produced yellow We now report on simple compounds with solutions. After filtration and precipitation with five-coordinated carbon atoms in cationic pentane/benzene crystalline complexes CH 3-C [A u P R 3]4 units. [H3C -C (A u P P h 3)4]+BF4- (1), [H3C -C (A u P { C 6H u }3)4]+BF4- (2) and Results [H3C -C ({ A u P P h 2CH 2CH 2}2C 6H 4)2]+BF4- (3) In preceding work tetrakis(dimethoxyboryl)- were obtained. methane C[B(OMe )2]4 and bis(dimethoxyboryl)- The products 1, 2 (yellow) and 3 (colourless) are m ethane H 2C[B(OM e)2]2 were found to be excel­ airstable, hygroscopic substances, insoluble in lent starting materials for the synthesis of highly non-polar solvents like pentane, slightly soluble in aurated homoleptic carbon centered clusters [4 c, benzene and readily soluble in dichloromethane or d, e-h]. Thus, the reactions of C[B(OMe )2]4 with HMPT. The compounds decompose on melting. (triorganylphosphine)gold(I) chlorides LAuCl in Characterization is achieved by elemental analysis, the presence of CsF lead to the formation of hy­ mass spectrometry and NMR spectroscopy. The percoordinated hexakis(phosphineaurio(I))-meth- data are summarized in the Experimental Section. anium(2+) dications of the type [(AuL) 6C]2+. The The existence of the hypercoordinated species degree of auration could be reduced from six to [CH3-C(A uPR3)4]+ was first established by high- five and four by the use of gold chloride complexes resolution field desorption (FD) mass spectrosco­ with bulky phosphanes [6 c], py. In the mass spectral studies the parent peaks at When l,l,l-tris(dimethoxyboryl)ethane was m /z = 1864.7 (1), 1936.1 (2), and 1821.1 (3) can chosen as the precursor, which is readily obtained readily be assigned to the appropriate cations. CH + 4 RjPAuCI. + 4 CsF H3C -C[B (O M e)2]3 b f 4- - 4 CsCI, - 2 (MeO)jB R p ^ A u " - / \~ " A u . ‘ PR-i 3 Au Au / \ Ph2 RjP PR3 + 4 CsF PAuCI - 4 CsCI 1 : R = Ph - 2 (MeO)3B ocx.Ph, 2 : R = c—C6H„ b f 4~ 74 Q. Steigeimann et al. • Tetraaurio(I) Complexes Table I. {'H}3IP NMR chemical shifts 6 [ppm] for com­ are also in good agreement with that found for pounds R3PAuCl and [CH 3-C (A uP R 3)4]BF4. (H 3C)3C -A u P P h 3 (V HP = 6.5 Hz). In the {'H}13C NMR spectrum of p r 3 R3PAuC1 [CH3C(AuPR3)4]BF4 [H3C -C (A u P P h 3)4]BF4 the resonances of the PPh-, 33.4 32.1 phenyl carbon atoms show a pattern also common P(C6H n )3 54.9 49.5 for homoleptic carbon centered gold cluster '/2(Ph,PCH,CH,) 2C6H4 29.2 27.5 cations. The doublet for the ipso C atom is shifted downfield as compared to the corresponding reso­ nance in Ph 3PAuCl, whereas the other phenyl sig­ The {'H } 3IP-NMR spectra at room temperature nals are largely unchanged. The o- and w-carbon of compounds 1 -3 in dichloromethane-d 2 show atoms give rise to centered doublets caused by long one sharp singlet resonance in each case, which is range P-P ' coupling. The resonance of the termi­ not only indicative of a virtual fourfold symmetry nal H3C group appears as a singlet at Ö = 28.2 ppm. of the cations of 1 and 2, but also demonstrates the The signal of the interstitial carbon could not be equivalence of the ligand halves in the chelated detected, and partial enrichment with ,3C will cation of 3. When compared to the data of the cor­ probably be necessary for a direct observation of responding (phosphine)gold(I) chlorides, upfield the nucleus, a procedure already successfully ap­ shifts can be stated (Table I), as already reported plied for the [C(AuL)6]:+ species [4f], for the conversion of (phosphine)gold(I) com­ pounds to homoleptic hypercoordinated species Crystal Structure Determinations [(AuL)5C]+ [4d], [(AuL)6C]2+ [ 4 c , e-h]. The equi­ valence of the LAu units is further established by Because of strong crystal disorder in all samples the number and multiplicity of the signals in the ’H of 1 so far investigated, only the C -C (A u-P )4 NMR spectra. Besides the resonances of the (phos- skeleton could be determined for the cation in phine) ligands, symmetrical 1:4:6:4:1 quintets [H3C -C (A u P P h 3)4]BF4, which crystallizes in the could be observed for the methyl hydrogen atoms at triclinic space group P i with two stoichiometric ö = 3.55 (1), 3.22 (2) and 3.65 ppm (3) due to a VHP equivalents in the unit cell excluding any crystallo- coupling with the phosphorus atoms of the phos- graphical symmetry for the individual cation.
Load more

Recommended publications
  • The Problem the Diols, Such As Ethane-1,2-Diol, Which Are The
    The problem The diols, such as ethane-1,2-diol, which are the products of the reaction with cold dilute potassium manganate(VII), are themselves quite easily oxidised by manganate(VII) ions. That means that the reaction won't stop at this point unless the potassium manganate(VII) solution is very dilute, very cold, and preferably not under acidic conditions. If you are using hot concentrated acidified potassium manganate(VII) solution, what you finally end up with depends on the arrangement of groups around the carbon-carbon double bond. Writing a structural formula to represent any alkene The formula below represents a general alkene. In organic chemistry, the symbol R is used to represent hydrocarbon groups or hydrogen in a formula when you don't want to talk about specific compounds. If you use the symbol more than once in a formula (as here), the various groups are written as R1, R2, etc. In this particular case, the double bond is surrounded by four such groups, and these can be any combination of same or different - so they could be 2 hydrogens, a methyl and an ethyl, or 1 hydrogen and 3 methyls, or 1 hydrogen and 1 methyl and 1 ethyl and 1 propyl, or any other combination you can think of. In other words, this formula represents every possible simple alkene: The first stage of the extended oxidation The acidified potassium manganate(VII) solution oxidises the alkene by breaking the carbon-carbon double bond and replacing it with two carbon-oxygen double bonds. 1 The products are known as carbonyl compounds because they contain the carbonyl group, C=O.
    [Show full text]
  • Abstract Superacid Catalyzed Reactions
    ABSTRACT SUPERACID CATALYZED REACTIONS: GENERATION OF REACTIVE INTERMEDIATES AND THEIR CHEMISTRY Makafui Gasonoo, Ph.D. Department of Chemistry and Biochemistry Northern Illinois University, 2017 Douglas A. Klumpp, Director This dissertation describes the use of triflic acid as catalyst for generating reactive intermediates and studying their reactivities under varying reaction conditions. The first chapter is an introduction to the types of organic reactions and acids. This chapter also discusses generation and reactivities of superelectrophiles as well. Chapter 2 discusses the synthesis of 3,3-disubstituted-2-oxindoles from the reaction of a series of acetonyl-substituted 3-hydroxy-2-oxindoles with arene in the presence of triflic acid. These reactions are performed under mild conditions and products isolated in decent yields. In chapter 3, the effects of charge migration in a tetra- and pentacationic superelectrophile is studied. These highly reactive intermediates are reacted with benzene at elevated temperatures. In the absence of benzene, cyclization occurs to produce novel N- heterocyclic compounds. Alcohol precursors are also ionized to generate these reactive intermediates and studied using low-temperature NMR. Chapter 4 talks about the effects of charge-charge repulsion on the aromaticity and anti- aromaticity in fluorenyl and dibenzosuberenyl cations respectively. These cations are generated from ionization of the respective biaryl ketones and dibenzosuberenols with superacid. With increasing charge, there is a corresponding increase in the aromaticity or anti-aromaticity of the respective system. Chapter 5 describes the superacid-promoted synthesis of heterocycle-containing 9,9- diarylfluorenes from biaryl ketones. Products are generally isolated in good yields using mild reaction conditions. Some of these compounds are used in the manufacture of organic light emitting diodes (OLEDs) and other organic-based electronics.
    [Show full text]
  • General Concepts in Organic Chemistry
    General Organic Chemistry-Part I 1 General Concepts in Organic Chemistry (A) Types of Organic Reactions: There six common types of organic reactions for the purpose of a beginner. (a) Substitution (b) Addition (c) Elimination (d) Oxidation (e) Reduction (f) Molecular Rearrangement Substitution Reactions: One group or atom is substituted by another group or atom. heat/ R H ++ Br R Br HBr 2 light R Br ++ KOH R OH KBr In the first example, H atom has been substituted by Br atom, so that an alkane is converted to alkyl bromide. In the second example, a Br atomm is substituted by OH group, so that an alkyl bromide has been converted to an alcohol. Addition Reactions: A double bond or a triple bond in a molecule gets added up with another molecule(addendum). Hence the unsaturation in the molecule is vanished or reduced. Br Br CH2 CH2 + Br2 CH2 CH2 Cl CH CH + HCl CH2 CH In the first example, an alkene(ethene) adds with a Br2 molecule, each carbon atom joins with one Br atom to give 1,2-dibromoethane. Thus the unsaturation is vanished. In the second example, alkyne(ethyne) adds onto one HCl molecule, one carbon joins with H atom and the other with Cl atom to give ethenyl chloride(vinyl chloride). Thus degree of unsaturation is reduced. Note that other conditions of the reactions are not given here. It is just an introduction. Elimination Reactions: One molecule is eliminated from the organic molecule to increase the degree of unsaturation. A saturated compound gives an alkene and an alkene gives an alkyne.
    [Show full text]
  • GLOSSARY of CLASS NAMES of ORGANIC COMPOUNDS and REACTIVE INTERMEDIATES BASED on STRUCTURE (IUPAC Recommendations 1995)
    Pure &App/. Chem., Vol. 67, Nos 819, pp. 1307-1375, 1995. Printed in Great Britain. (B 1995 IUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY ORGANIC CHEMISTRY DMSION COMMISSION ON NOMENCLATURE OF ORGANIC CHEMISTRY (III. 1) COMMISSION ON PHYSICAL ORGANIC CHEMISTRY (III.2) GLOSSARY OF CLASS NAMES OF ORGANIC COMPOUNDS AND REACTIVE INTERMEDIATES BASED ON STRUCTURE (IUPAC Recommendations 1995) Prepared for publication by G.P. MOSS, P.A.S. SMITH and D. TAVERNIER Cornpodtion of the ZZZ.1 & 111.2 Working Party (1980-1994): H.J.T. Bos, A.J. Boulton, E.W. Godly, P. Griinanger, A.D. McNaught, G.P. Moss, R. PanicO, J. Rigaudy, P.A.S. Smith (Conwnorfiom ZZZ, I), J.H. Stocker, D. Tavernier, R.A.Y. Jones, J. March, J.M. McBnde, P. Miiller (Conwnorfim 111.2). Membership of the Commission on Nomenclature of Organic Chemistry during the preparation of this document (1980-1994) was as follows: Titular Members: 0. Achmatowicz (Poland) 1979-1987; H. J. T. Bos (Netherlands) 1987- , Vice-Chairman, 1991- ; J. R. Bull (Republic of South Africa) 1987-1993; H. A. Favre (Canada) 1989- , Chairman, 1991- ; P. M. Giles, Jr. (USA) 1989- ; E. W. Godly (UK) 1987-1993. Secretary, 1989-1993 ; D. Hellwinkel (Federal Republic of Germany) 1979-1987, Vice- Chairman, 1981-1987; B. J. Herold (Portugal) 1994- ; K. Hirayama (Japan) 1975-1983; M. V. KisakUrck (Switizrland) 1994- ; A. D. McNaught (UK) 1979-1987; G. P. Moss (UK) 1977- 1987, Chairinan, 1981- 1987, Vice-Chainnun, 1979-1981; R. Panico (Francc) 1981-1991, Vice- Chairman, 1989-1991; W. H. Powell (USA) Secretary, 1979-1989; J.
    [Show full text]
  • WO 2016/171769 Al 27 October 2016 (27.10.2016) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2016/171769 Al 27 October 2016 (27.10.2016) P O P C T (51) International Patent Classification: land, WA 99354 (US). CHOUYYOK, Wilaiwan G01L 5/(94 (2006.01) [US/US]; 2177 Crestview Avenue, Richland, WA 99354 (US). ATKINSON, David A. [US/US]; 178 Sell Lane, (21) International Application Number: Richland, WA 99354 (US). PCT/US20 16/00003 8 (74) Agent: PAYNTER, Leland Scott; Leland Scott Paynter IP (22) International Filing Date: Law LLC, 7730 North Whittier Place, Indianapolis, IN 2 1 April 2016 (21 .04.2016) 46250 (US). English (25) Filing Language: (81) Designated States (unless otherwise indicated, for every (26) Publication Language: English kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (30) Priority Data: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, 14/692,371 2 1 April 2015 (21.04.2015) US DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, 14/692,460 2 1 April 2015 (21.04.2015) US HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (71) Applicant: BATTELLE MEMORIAL INSTITUTE KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, [US/US]; 902 Battelle Blvd., P.O. Box 999, Richland, WA MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, 99352 (US). PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, (72) Inventors; and TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
    [Show full text]
  • Scy1112 General Chemistry Ii
    School of Science and Humanities Department of Chemistry SCY1112 GENERAL CHEMISTRY II Unit 1 Analytical Methods Classification of analytical methods, advantages of instrumental methods - Qualitative Inorganic Analysis: Dry test, flame test, Cobalt nitrate test - Wet confirmatory tests for acid radicals - Interfering acid radicals- Theory of Interference- Elimination of Interfering acid radicals. Gravimetric analysis: mechanism of precipitation – solubility products –common ion effect – Types of precipitation – co-precipitation and post precipitation – homogeneous precipitation - General rules for precipitation Effect of digestion - washing of precipitates- Drying of precipitates Types, care and use of crucibles. 1. Introduction: Analytical chemistry is the study of the separation, identification and quantification of the chemical components of natural and artificial materials. Analytical chemistry has applications in forensics, bioanalysis, clinical analysis, environmental analysis and materials analysis. Qualitative analysis is a method of analytical chemistry that deals with the determination of elemental composition of inorganic salts. It is mainly concerned with the detection of ions in an aqueous solution of the salt. For example, golden yellow in flame test shows the presence of sodium. Analytical methods can be separated into classical and instrumental. 1.1 Classical Methods: • Separation are performed by precipitation, solvent extraction or distillation. • Quantitative analysis performed by gravimetric and volumetric methods. • Detection limits are in the ppm range. • Precision can often be excellent. • These methods are often labor intensive. 1.1.1 Classification of Analytical Methods: The main techniques employed in quantitative analysis are based upon (a) The quantitative performance of suitable chemical reactions and either measuring the amount of reagent needed to complete the reaction, or ascertaining the amount of reaction product obtained (b) Appropriate electrical measurements (e.g.
    [Show full text]
  • Synthesis, Structure, and Reactivity Studies of Ketenylidene, Carbide, Carbynoid, Carbenoid, and Tetrazolyl Complexes of Gold
    SYNTHESIS, STRUCTURE, AND REACTIVITY STUDIES OF KETENYLIDENE, CARBIDE, CARBYNOID, CARBENOID, AND TETRAZOLYL COMPLEXES OF GOLD A Dissertation Presented to The Academic Faculty by Nicholas T. Daugherty In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry and Biochemistry Georgia Institute of Technology August 2018 Copyright © 2018 by Nicholas T. Daugherty SYNTHESIS, STRUCTURE, AND REACTIVITY STUDIES OF KETENYLIDENE, CARBIDE, CARBYNOID, CARBENOID, AND TETRAZOLYL COMPLEXES OF GOLD Approved by: Dr. Joseph P. Sadighi, Advisor Dr. Z. John Zhang School of Chemistry and Biochemistry School of Chemistry and Biochemistry Georgia Institute of Technology Georgia Institute of Technology Dr. Angus P. Wilkinson Dr. Carsten Sievers School of Chemistry and Biochemistry School of Chemical and Biomolecular Georgia Institute of Technology Engineering Georgia Institute of Technology Dr. Jake D. Soper Dr. Christopher W. Jones School of Chemistry and Biochemistry School of Chemical and Biomolecular Georgia Institute of Technology Engineering Georgia Institute of Technology Date Approved: May 2, 2018 To my wife, Veronica Daugherty ACKOWLEDGEMENTS I thank my research advisor, Professor Joseph Sadighi, for the opportunity to work and learn in his research group. Joseph has taught me a great deal about developing strategies for making and breaking bonds, and he has set an example of honest, responsible, dedicated leadership. Joseph is truly interested in the success of his students, not only in terms of the science, but also at a personal level. I also want to thank Joseph for the occasional cup of coffee and unexpected group-meeting reference to Monty Python. It has truly been a pleasure to work for him.
    [Show full text]