Reactions of gold(I) electrophiles with nucleophiles derived from group 6 Fischer-type carbene complexes

dc.contributor.advisorRaubenheimer, H. G.en_ZA
dc.contributor.authorEsterhuysen, Matthias Wilhelmen_ZA
dc.contributor.otherUniversity of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer science
dc.descriptionDissertation (PhD)--University of Stellenbosch, 2003.en_ZA
dc.description.abstractENGLISH ABSTRACT: This study comprises the preparation and characterisation of various novel organometallic species of gold(I) by employing a range of anionic group 6 metal Fischer-type carbene complexes and group 6 metal-acyl complexes as synthons of the organic moieties introduced to the gold(I) electrophiles. The main objectives of this work are to develop the use of Fischer-type carbene complexes as synthons in the preparation of novel organometallic species along unusual reaction pathways and, in doing so, to expand the organometallic chemistry of gold(I), especially Au-C bond formation reactions. By reacting various β-CH acidic Fischer-type alkoxy/dialkylamino/ alkthio(methyl)carbene complexes, first with a base, and then with a gold(I) electrophile (Ph3PAu+), easy access to vinyl ether/dialkylamine/thioether complexes of gold(I) coordinated to M(CO)5 (M = Cr, Mo, W) fragments, is obtained. When methyl alkoxy- or dialkylaminocarbene complexes are employed, coordination of the novel alkoxyvinyl-gold(I)PPh3 and dialkylaminovinyl-gold(I)PPh3 species to the M(CO)5 fragments occurs in an asymmetrical fashion through the vinyl functionalities of the novel gold(I) species. This usually unstable coordination mode for vinyl ethers is stabilised by delocalisation of partial positive charges from the α-gold vinyl carbon atoms to either the gold(I)PPh3 fragment [for η2-{alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes] or the nitogen atoms of the vinyl amine group [for η2-{dialkylaminovinylgold( I)PPh3}M(CO)5 complexes]. In the latter complexes this delocalisation occurs to such an extent that these complexes are best described as zwitterions. The corresponding negative charges in the bimetallic complexes reside on the M(CO)5 fragments. As a representative example, uncoordinated ethoxyvinyl-gold(I)PPh3 was isolated in high yield via a ligand replacement reaction with PPh3. When Fischer-type alkthio(methyl)carbene complexes are employed in this conversion, novel sulphur coordinated {alkthiovinyl-gold(I)PPh3}Cr(CO)5 complexes are formed.The reaction mechanism involved in these conversions is believed to be the gold(I) analogue of the hydrolysis of Fischer-type carbene complexes. In this mechanism the bimetallic η2-vinyl ether coordinated {alkoxyvinyl-gold(I)PPh3}M(CO)5 complexes represent stabilised gold(I) analogues of postulated transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. The term aurolysis is conceived to describe the conversion when Ph3PAu+ is employed as electrophile instead of H+. The formation of the bimetallic η2-vinyl ether coordinated complexes in the current conversion, furthermore, strongly supports the existence of similar transition states in the hydrolytic decomposition of Fischer-type alkoxycarbene complexes. This mechanism is also accepted for the formation of analogous η2-{dialkylaminovinyl-gold(I)PPh3}M(CO)5 and {alkthiovinyl-gold(I)PPh3}-S Cr(CO)5 complexes when β-CH deprotonated Fischer-type dialkylamino- and alkthiocarbene complexes are employed in this reaction. The reaction of anionic group 6 metal-acyl complexes and their nitrogen analogues, N-deprotonated Fischer-type aminocarbene complexes, leads to the formation of acylgold(I) and novel imidoylgold(I) complexes coordinated to M(CO)5 (M = Cr, W) fragments. In the previous complexes poor stabilisation of the M(CO)5 fragments allows halide anions to readily form ionic adducts with these groups. This characteristic of these products provides a useful reaction pathway to the first example of a free acylgold(I) complex, benzoyl-AuPPh3. Coordination of the imine nitrogen atom to the M(CO)5 fragments in the analogous bimetallic imidoylgold(I)-M(CO)5 complexes is much stronger. These complexes are remarkably stable and could even be effectively isolated by means of low temperature silica gel chromatography. As a preliminary reaction mechanism for this conversion we propose a mechanism that is closely related to the aurolysis mechanism described above. The only difference is that, instead of formal reductive elimination of vinyl ethers/amine/thioether complexes of gold(I) from the M(CO)5 fragments, acyl and imidoyl complexes of gold(I) are produced in this step. Furthermore, the (Z)- stereoisomers of the bimetallic imidoylgold(I)-M(CO)5 complexes generated in this conversion are exclusively obtained.A second N-deprotonation-auration reaction sequence performed on suitable examples of the bimetallic imidoylgold(I)-M(CO)5 complexes yields, as the only isolable product, a novel triangular Au2Cr cluster complex, cis-{η2-(Ph3PAu)2} PPh3Cr(CO)4. This complex is the isolobal equivalent for the unstable molecular hydrogen complex, (η2-H2)PPh3Cr(CO)4, and exhibits the shortest known Au-Au separation between two gold atoms in cluster complexes of the type Au2M. Finally, two novel and vastly different molecular structures of closely related anionic benzoylpentacarbonyl tungstates, one with Li+ as counterion and another in which exactly half the Li+-cations have been replaced by protons, highlight the importance of hydrogen bonding and ion-dipole interactions in determining the solid state structure of such complexes.en_ZA
dc.description.abstractAFRIKAANSE OPSOMMING: Hierdie studie behels die bereiding en karakterisering van verskeie nuwe organometaalkomplekse van goud(I). Hierdie komplekse is berei deur gebruik te maak van n wye reeks anioniese groep 6 metaal Fischer-tipe karbeenkomplekse asook anioniese groep 6 metaal asielkomplekse as sintetiese ekwivalente vir die organiese fragmente wat gedurende die sintese aan die goud atoom gebind word. Die hoofdoel van hierdie studie is om die gebruik van Fischer-tipe karbeenkomplekse as sintetiese voorgangers in die bereiding van nuwe organometaalverbindings te ontwikkel en om sodoende ook die organometaalchemie van goud verder uit te bou. Veral die ontwikkeling van nuwe sintetiese metodologieë vir die bereiding van Au-C bindings is hier van belang. Verskeie Fischer-tipe alkoksie-/dialkielamino-/alktio-(metiel)karbeenkomplekse met suuragtige waterstofatome geleë op die β-metallo-koolstofatoom is eers onomkeerbaar gedeprotoneer. Byvoeging van die goud(I) elektrofiel, Ph3PAu+, lei - volgens n ongewone reaksiemeganisme - tot die vorming van onderskeie vinieleter-, dialkielvinielamien- en vinieltioeterkomplekse van goud(I). Hierdie komplekse is verder ook op verskillende wyses aan M(CO)5 fragmente (M = Cr, Mo, W) gekoördineer. Die vinieleter- en vinielamienkomplekse van goud(I), wat vorm wanneer alkoksie- en dialkielaminokarbeenkomplekse onderskeidelik in hierdie sintese aangewend word, koördineer onsimmetries deur hulle viniel dubbelbindings aan die vrygestelde M(CO)5-groepe. Hierdie normaalweg onstabiele vorm van vinieleterkoördinasie, word gestabiliseer deur delokalisering van positiewe lading vanaf die α-goud viniel koolstofatoom na die AuPPh3-fragment [vir die η2-{alkoksievinielgoud( I)PPh3}M(CO)5 komplekse] óf na die stikstofatoom van die dialkielvinielamien groep [vir die η2-{dialkielaminoviniel-goud(I)PPh3}M(CO)5 komplekse]. Laasgenoemde komplekse kan as zwitterione beskryf word. Die onderskeie negatiewe ladings in hierdie komplekse bevind hulle hoofsaaklik op die M(CO)5 groepe. Sterk koördinerende ligande (bv. PPh3) verplaas die onsimmetriese viniel eter vanaf die M(CO)5-fragment. Só kon, as n voorbeeld, die vrye etoksievinielgoud( I)PPh3-kompleks met n hoë opbrengs berei word. Wanneer β-gedeprotoneerdeFischer-tipe tiokarbeenkomplekse met Ph3PAu+ reageer, vorm swawel gekoördineerde {tioviniel-goud(I)PPh3}Cr(CO)5 bimetalliese komplekse in stede van die π-komplekse. Dit word voorgestel dat in die bogenoemde reaksies die goud(I)elektrofiel dieselfde rol vervul as die proton gedurende die hidrolise van Fischer-tipe alkoksiekarbeenkomplekse. Die bimetalliese, η2-vinieleter-gekoördineerde {alkoksieviniel-goud(I)PPh3}M(CO)5-komplekse hier berei verteenwoordig dus stabiele goud(I) analoë van voorgestelde tusseprodukte in so ’n meganisme. Die term aurolise word voorgestel om die geval waar Ph3PAu+ in stede van H+ as elektrofiel aangewend word te beskryf. Die vorming van bimetalliese, η2-vinieletergeko ördineerde komplekse in die huidige reaksie ondersteun die moontlike vorming van die voorgestelde tussenprodukte tydens die hidrolise van Fischer-tipe alkoksie(metiel)karbeenkomplekse. ’n Soortgelyke meganisme kan ook gebruik word om die vorming van die η2-{dialkiellamienviniel-goud(I)PPh3}M(CO)5- en {alktioviniel-goud(I)PPh3}-S Cr(CO)5-komplekse vanuit β-CH gedeprotoneerde Fischer-tipe dialkielamino- en tiokarbeenkomplekse en Ph3PAuCl te interpreteer. Die reaksie van anioniese groep 6 oorgangsmetaal metaal-asielkomplekse en hulle stikstofanaloë, N-gedeprotoneerde Fischer-tipe aminokarbeenkomplekse, lewer onderskeidelik asiel- en imidoielkomplekse van goud(I) wat aan M(CO)5 fragmente (M = Cr, W) koördineer. Die goud(I)asiel-M(CO)5 koördinasie deur die asielsuurstofatoom is baie swak en die M(CO)5-eenheid in hierdie komplekse word maklik deur haliedanione en sekere oplosmiddel molekules verplaas. Die haliedanione vorm anioniese addukte met the M(CO)5 fragmente. Hierdie eienskap van die bimetalliese komplekse verskaf sodoende n gerieflike sintetiese roete na die eerste voorbeeld van n vrye asielgoud(I)-kompleks, bensoiel-AuPPh3. Koördinasie van die imienstikstofatoom aan M(CO)5-groepe in die bg. imidoielkomplekse is egter veel sterker. Die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse is verbasend stabiel en kan selfs effektief deur middel van lae temperatuur SiO2-kolomkromatografie geïsoleer word. n Soortgelyke reaksie meganisme as wat voorgestel word vir die aurolise van Fischer-tipe karbeenkomplekse word voorgestel vir hierdie reaksie. Die enigste verskil is dat die formele reduktiewe eliminasie van n viniel-eter, -amien of -tioeter vervang word met die vorming van asiel- of imidoielkomplekse van goud(I). Verder word die (Z)-isomere van die bimetalliese {imidoielgoud(I)}M(CO)5-komplekse uitsluitlik in hierdie reaksie verkry. Wanneer geskikte voorbeelde van bimetalliese {imidoielgoud(I)}M(CO)5-komplekse n tweede keer gedeprotoneer word en gereageer word met Ph3PAuCl, is die enigste isoleerbare produk van die reaksie n driehoekige Au2Cr troskompleks, nl. cis-{η2- (Ph3PAu)2}PPh3Cr(CO)4. Hierdie verbinding dien as n isolobale model vir die onstabiele molekulêre waterstof kompleks , (η2-H2)PPh3Cr(CO)4, en besit verder die kortste Au-Au afstand tussen twee goud atome in driehoekige troskomplekse wat nog tot dusvêr gerapporteer is. Laastens is die kristalstrukture van twee nou verwante anioniese {bensoiel}W(CO)5- komplekse bepaal. Die enigste verskil tussen die hierdie twee verbindings is dat die een slegs Li+ as teenioon bevat terwyl presies die helfte van die Li+-teenione in die tweede struktuur deur protone verplaas is. Hierdie klein verskil in samestelling veroorsaak egter drastiese verskille in die kristalstrukture van hierdie verbindings. Die belangrikheid van waterstof bindings en ioon-dipool interaksies in die bepaling van die vastetoestandstrukture van sulke verbindings word hierdeur beklemtoon.en_ZA
dc.format.extentxvii, 189 leaves :ill.
dc.publisherStellenbosch : University of Stellenbosch
dc.subjectCarbenes (Methylene compounds)en_ZA
dc.subjectMetal complexesen_ZA
dc.subjectMetals -- Analysisen_ZA
dc.subjectChemical reactionsen_ZA
dc.subjectTheses -- Chemistryen_ZA
dc.subjectDissertations -- Chemistryen_ZA
dc.titleReactions of gold(I) electrophiles with nucleophiles derived from group 6 Fischer-type carbene complexesen_ZA
dc.rights.holderUniversity of Stellenbosch

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