Neue Halogenowolfram(+VI) carbine durch chlorierende oxidation, synthese des ersten fluorowolfram(+VI) carbin-Komplexes

Abstract

Carbonyl carbyne complexes [L R(CO) 2WC- p-tol], containing the tripodal oxygen ligands L R −=[(C 5H 5)Co{P(O)R 2} 3] −, R  OMe, O iPr, are oxidised by iodobenzene dichloride (PhICl 2) to yield the chloro carbyne complexes [L RCl 2WC- p-tol]. The reaction of the carbonyl carbyne complexes [L R(CO) 2MoC- p-tol] with PhICl 2 leads to the molybdenum complexes [{L OMeMoCl 2} 2] and [L RMoCl 4], R  OMe, O iPr. Treatment of [L OMeCl 2WC- p-tol] with [Me 3SnF] affords [L OMeF 2WC- p-ol], the first example of a Schrock carbyne complex bearing fluoride ligands. In order to test the reactivity of the new fluoro carbyne complex, reactions with NaOEt and Me 3SiNMe 2 have been performed. With NaOEt both fluoro ligands in [L OMeF 2WC- p-tol] are substituted to yield [L OMe(OEt) 2WC- p-tol]. With Me 3SiNMe 2 in toluene, [L OMeF 2WC- p-tol] reacts to yield the complex [L OMeF(NMe 2)WC- p-tol]. When the reaction is performed in dichloromethane, [L OMeCl(NMe 2)WC- p-tol] is isolated.