ln+õe CV C LOPENT AOTENV L RUÍHEÑTUM CHEMTSÍRY *** bq Robu,t Cha¡Le's wa,U'U 8.Sc. lHows.) r** A The'si's pneterttød {on thø løgnøe od OocÅon o( Plvílc:.sop|tq Thø Oeytantnønf o( PLtqaLcal and InongawLe Cheni'sfnq The. UwLvetui-tq o6 Ade-La,Ldø Junø I98l I ,\ - I f l, . 1, ,-ei Jì ;.-', ,ìi I ì v'ri.t, -, i{ .f f¡. I 'i i, Ì i,.ov'ao,i.l. ¡t r i,', , j.l , il I ì:1r,'ì ' ,,1,{ ., TAßLE OF CONÍENTS SECTÍON A. CHAPTER 1. A SUMMARY OF THE CHEMISTRV OF CARB(0NYL.FREE COMPLEXES OT THE TYPE RuX(PRs) z(n-CsHs ). Røa"e-LLowt o d tltø l'le,tß..L- tla'Logøn Bond 5 Líga.nd Exelnng ø Røacfio nt 6 Ca.tionie CompX.exe's I Røaetíoyu o[ RuR(PPhs)z (n-Csfls ) t0 (A) Cqc,[.omefa'L[-a-.tion R¿ac.tiorø 10 (B) Rza.cfion¿ w,í,th EX-øcfnctn-dø(¡icLenf. )Lødiru t4 and A,Llzqne.r Aeutq[idø CompLexe's 29 CHAPTER 2, CV C L??ENT AO T ENV L-RUT HENI UMt AN, - 0SMI UI,l CHEtr {I STRV, 3)îÁPLEXES C0NTA/^JING NITRILES, IS0NITRILES, TERTIARy PÍI0SPINES ANO PHOSPHTTES F,RMEO ßY AYOTTTON ()R DTSPLACE¡,,IENT REACT/ONS. lntnoducbLon 3l ReacÍ.cowt wí.th N'í.tní,Le's 32 RearLLon wífh TnLdluonoa"ce,tovt/if)ú't-e- 38 R¿ae,LLont a$(ond"Lng l¿oru.Í¡i.(-e Comp,Lexe's 43 Røq.oLLon's wi-th Te,nLLanq Pho,sphine's a"nd Phodptuíføt 45 Oi'scu.¿¿ion 49 Expwínønta.L 53 0HATrER 3, CV C L?PENT AOI ENV L-RUT HENI Ul,tl AN, - OSM I ul'l CHEMI STRV . }IMPLEXES C0NTAÍNING SoME SUBSTITUTED nr -VTNVLIDENE, nt-AceTVLIDE AN? cARBENE LTGANDS, lntttodue.tion 73 llo no,s ub ¿ t ífufed nr - V ínqt-Ldene C omp,Løxe's 80 Subrriiut¿d nL - EthqnqL C ompLøxat 82 Sqnthus.t.t oó nL -Vinqlidøne DetúvaüLve's $tom rl -tthqnqX- 83 ComytL-exe,t Reac.tion¿ be,tu¿øn Ru(czPh) QPI+z )z (n-CsHs ) and Ttr.he'thtqL 85 Plto'splu<fø RøacLLon be-tw¿øn 4^H qnoxqpønl' l' qnø and 85 RuCLQPhz,)z (n-Csfls ) t (PP ( 88 T he Røctc.tio n b efw e.¿n {Ru(C = CHP l,L) h s )z n - C s Él s ) } and Dioxqgøn Oi'Scu.t¿íon 88 Expwínønta,[- 96 cHAn'ER 4, Cy C L1PENT A0 I ENV L-RUT HENI UM AN2 - 0-qM I Ul'tí CHEl"lI STRV . COMPLEXES CONTATNTNG CYANOCARB()N AN? CYANONITROGEN LTGANOS. lyúnodue.tion It5 Retsu.U's n7 Oi,tcu.t¿ion 125 Expuúnewta,L 129 CHANER 5, r3c N.^,1.R. srurfEs 0F s)ME :V:L)PENTAqTENVL-RUTHENTUM AND .OSMTUM COI,,IPLEXES IntltoductLon 132 Di,tcu¿¿íon 139 REFERENCES - SECTTON A 147 sEcÏlo/\' B. CHAWER 6, DOOEC AC ARßri NV LTRIRUT HENT UI,Ä CH EI'II ST RY . REACTTONS ßETWEE.N RUTHENIUI,II CAREONYL AND TSOCYANI'ES. IvttnoductLon 156 Reto-LLont od Rut (C0)r 2 wi-th T,soeqawLdus 160 Cntlarnt and. Mole.u'Lan SUarc.tunø o ( Rus(CO) r r (CltJBat) 162 Reao.LLona oI Rut (C0) r r (CNß¿t) 167 Røao-tLon o( Rut (c0h(cNBut) and. R¿¿3(cO)re(cl,l8at)z 168 wi-th diltqdnogøn Pqno,(-qti-,s oI Ruz(C0) r r (CNBat) t7t Sqnthu.ts o( Rut (C0) r z 175 , Røacfioru o[ Rut (C0)r z whh ¿omø Gnoup V Ligand,s t75 Reao-tiowt o d H+RI+(C0) r z t76 Expuunørvta..t 178 REFERENCES - SECTION 8 t93 APPENDIX T, tq7 SUMMARY Section A of this thesis discusses the chemistry of the carbonyl- free complex RuCI(PPhs )r(¡-CsHs ) r detaiJ-ing reactions involving (i) reactions of the metal-halogen bond (ii) ligand exchange reactions and (iii) reactions affording cationic complexes. A variety of other cationic complexes are obtained vith nitrilest isonitriles, tertiary phosphines and phosphiLes, together rvith some observations on the relation betrueen ease of addition and repJ-acement ofl ligands in the formation of these cations. Reactions betureen terminal acetylenes HCzR and RuCl.(PPhg)r(¡-C5Hs) afford the monosubstituLed vinylidene complexes {Ru(C=CHn)(ppna)z(n-CsHr)}* (I), ruhich are readiJ.y deprotonated by bases to give the corresponding o-aceLyIides, Ru(C=cR)(pphs)2(¡-CsHs) {R = Me, Pr, Ph, CeH+F-4, CeFst CgzMe]. The o-acetylides react vith strong non-coordinating acids, such as HBF,* or HPFo, and also ryith tria].kyloxonium salts, such as {Mes0}PFe t to give the complexes (I), and {Ru(c=cnR')(pPns)z(n-csHs)}* (rr; Rr - Me, Et), respectively. The structure of (II; R = R'= Me) has been deternlined. Ligand exchange reactions of the o-acetylides afflord complexes Ru(C=CR)(L)(PPh3)(n-CsHs), Ru(C=CR)(L)z(¡-C5Hs) {L = PRs, P(0R)¡} and Ru(C=CR)(Lz)(n-CsHs) {Lz = dppe, dppm}, vhich can also be converted to the analogous vinylidene complexes. The reacLion betureen HCzCHzCHMeOH and RuCl(PPh¡)z(n-CsHs) does not afford a vinylidene complex; instead intramoLecular cyclisation to a complex containing the methyl substituted oxacycJ.opentyJ-idene ligand occurs spontaneously. This carbene is very reactive, undergoing a rapid base-catalysed H-D exchange at the carbon adjacent to the metal-bonded carbon. The reactions of severaf cyanocarbon and cyanonitrogen anions ulith the complex RuCI(PPhg)z(n-CsHs) are reported, in urhich the chloride is exchanged for the cyano-substituted grouP. lile are not a\uare of any other compounds containing these anions and organometallic residues. I3C The last chapter Ín Section A discusses the spectra of the products obtained above. V'le had envisaged a relationship betveen the 13C and rH resonances of the cycJ.opentadienyl tigand and vanted to note the chemical shift values of various Ru-C carbons. SecLion B of this thesis discusses the chemistry of the cluster carbonyl Rug (C0)rz. l'Jith feru exceptions, substitution of Ru¡ (C0)rz by Group V donor ligands, L, affords the trisubstituted complexes Ru3(C0)gLs, in ruhich one C0 group on each melal atom has been displaced by the ligand molecuLe. .Triruthenium dodecacarbonyl reacts vith BuÍNC under mild conditions to give Rua(C0)rr(CNgul) (III), a fluxional moLecule ruhich adopts the axialty substituted structure in the solid state. The unusual tvisting of, the Ruz(C0)s fragment in (III) has relevance to the current theories of fluxionality in cluster carbonyls. Di- and tri-substituted products are obtained using more vigorous reaction conditions. TetranucÌear hydrido complexes HaRu4(C0)rz-n(CNBul)¡ {n = 1-4} are formed from HqRuq(C0)rz. Complex (III) reacts vith dihydrogen in inert solvents to give mixtures of HRua(C0)g(p-HC=NBul¡, HRua(C0)a(CNBu¿)- + (p-HC=NBu¿), and an intermediate vhÍch reacts to give H+Ru+(C0)rz-n(CNBuÍ)n {n = 0-2}. Similar complexes u/ere formed in reactions betureen Rus(C0)ro(CNBuÍ)z and Hz. Complex (III) reacts vith Group V donor ligands to give the monosubstiLuted Rua(C0)rrL complexes and mixed ligand complexes, Rua(CO¡r0(CNBu¿)L. Pyrolysis of Ru3(C0)rr (CNBuÍ) affords Rus(C0)r+(CNBuÉ)2, ruhich contains an open rsvallotur cluster, urith one isocyanide ligand acting as a six-electron donor, and bonded to four of the five metal atoms. STATEMENT TluU thØ6i-a coyú,aiyur no møtu,LaL wltLch hars been aecepted don the atund od anq othuc døgteø on d,Lploma ín anq UwLvua.ifq and, to tttø bøot oó mA bnowledge and bel,Le(, coyttøLyø no mafuuLal pnøvíocuX,q publithød o,L tilÌ1,í,t-ten bq anothett pelutan, excøpt whUrc due nødUtønce. .íÀ madø in thø tøxÍ. o( thÍ's fhe'si's. R. C. ft,lA¿LIS ACKNOWLEOGEÄ,{EI(TS I would LLI¿ø to thanb mA Pnode'saon M. I. Btrttcø, óon ^upQivi's0n, hi.¿ encoUta"gemerú., guidance and he.Lp dwuLng the eoutt¿ø o( th,í'S u)orLb,' The o¿¿.t¿lnncø a.nd (nLøn&sluLp oó mU 6øtLow netøattch wonl¿etu lu,a been gnøa.flq appnzoLafød, Mq fhanh,s ane duø o'[to to Ju,LLø and nq mothut {on tqytíng ttLi's naru'setipt. A Commowea.L,th PoAtgnadua.te Awo"¡cd .í's gnat.ødu,U.g a"clznowlødgød. ABBREUTATTdNS In Experimental Section: Infrared Spectroscopy (I.R. ) m medium s strong TU veak vsr etc. very strong, sh shouLder Nuclear Magnetic Resonance Spectroscopy (N.M.R.) d doublet m multipJ-et q quartet qu quintet S singlet se sextet t triplet dof i, etc. doubl-et of triplets, Mass Spectrometry lrl mofecuLar rveight or ion ml e- molecufar ion 0thers C. approximately h hour min minute mg milligram MI millilitre fIì. p. melting point s second Chemical- Abbreviations throuqhout Text L Bu¿ tertiary butyJ. Cp cyclopentadienyl Cy cyclohexyl dpPe I, 2-bis ( diphenylphosphino ) ethane dppm bis ( diphenylphosphino ) methane EI ethyl Pr propyl Ph phenyl R alkyl and/or aryl tosmic pa.tLa"-toluenesu lphonylmethyl isocyanide X halogen CHAPTER 1 A SUAIMÁRY OF THE CHEI'|ISTRY OF CARßOI\/YL-FREE COI,,IPLEXES OF THE TY?E R¿rX(PRs)2(¡-C5Hs) Studies I t2 on ruthenium complexes containing both ¡-cyclopen and carbonyl ligands have shoun that. there is surprisingly little difference in reactivity betueen these complexes and the analogous iron- containing compounds. Hovever, the increased reactivit,y tovards small molecules of phosphine complexes compared vith those containing carbonyl groups, together ruith the useful-ness of some ruthenium(II) complexes 1n many catalytic reactions, 3 suggested that a study of the chemistry of carbonyl-free complexes of the type RuX(enr¡z(n-CsHs) uould be urorthurhil-e.