Fischer-type tungsten acyl (carbeniate), carbene and carbyne complexes bearing C5-attached thiazolyl substituents: Interaction with gold(I) fragments

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dc.contributor.authorStrasser C.E.
dc.contributor.authorCronje S.
dc.contributor.authorRaubenheimer H.G.
dc.date.accessioned2011-05-15T16:05:14Z
dc.date.available2011-05-15T16:05:14Z
dc.date.issued2010
dc.description.abstract2-(1-Piperidinyl)thiazole and 2-phenylthiazole were deprotonated at C5 of the thiazole rings and both reacted with [W(CO)6] to form Fischer-type tungsten carbeniate complexes 1a and 1b of the type [(CO 5)WC(O){C=CHN=C(R)S}] (R = 1-piperidinyl for 1a and phenyl for 1b). Reaction of carbeniate 1b with [(Ph3P)AuCl] afforded by acyl ligand transfer a tungstenoxycarbene complex of gold(I), [(Ph3P)Au=C{OW(CO) 5}{C=CHN=C(Ph)S}] (2), in which the W(CO)5 fragment remains coordinated to the acyl oxygen atom. Alkylation of 1a and 1b with [Me3O][BF4] afforded the carbene complexes [(CO) 5WQC(OMe){C=CHN=C(R)S}], 3a and 3b. A rare example of a hydroxycarbene complex of 1a stabilised by a hydrogen bond to 1a, [NMe 4][{S(R)C=NCH=C }C{=W(CO)5}OH...(O)C{W(CO) 5}{C=CH=C(R)S}], 4, (R = 1-piperidinyl) was crystallised while attempting to prepare 3a by a different route. Reaction of 3b with [ClAu(tht)] (tht = tetrahydrothiophene) furnished the corresponding alkoxycarbene gold(I) complex [ClAuQC(OMe){C=CHN=C(Ph)S}], 5. Subsequent reaction of 1a and 1b with bis(trichloromethyl)carbonate and pyridine yielded the carbyne complexes [Cl(CO)2(py)2W≡C{C=CHN=C(R)S}], 6a and 6b. Reaction of 6a with [ClAu(tht)] afforded an unstable addition compound, 7, in which the gold atom is coordinated to the formal carbyne triple bond. Interaction between gold and the proton of the thiazole ring in this complex was observed by variable temperature NMR. The crystal and molecular structures of complexes 1a, 1b, 2, 3b, 4, 5, 6a and 6b were all determined by single crystal X-ray diffraction. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010.
dc.description.versionArticle
dc.identifier.citationNew Journal of Chemistry
dc.identifier.citation34
dc.identifier.citation3
dc.identifier.issn11440546
dc.identifier.other10.1039/b9nj00413k
dc.identifier.urihttp://hdl.handle.net/10019.1/13036
dc.subjectbarban
dc.subjectcarbene
dc.subjectgold
dc.subjectmetal complex
dc.subjectphenyl group
dc.subjecttetrahydrothiophene derivative
dc.subjectthiazole derivative
dc.subjecttungsten carbeniate
dc.subjecttungsten derivative
dc.subjectunclassified drug
dc.subjectalkylation
dc.subjectarticle
dc.subjectcarbon nuclear magnetic resonance
dc.subjectchemical modification
dc.subjectchemical structure
dc.subjectcontrolled study
dc.subjectcrystal structure
dc.subjecthydrogen bond
dc.subjectinfrared spectroscopy
dc.subjectmass spectrometry
dc.subjectmolecular interaction
dc.subjectpriority journal
dc.subjectproton nuclear magnetic resonance
dc.subjectproton transport
dc.subjectX ray crystallography
dc.subjectX ray diffraction
dc.titleFischer-type tungsten acyl (carbeniate), carbene and carbyne complexes bearing C5-attached thiazolyl substituents: Interaction with gold(I) fragments
dc.typeArticle
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