Isonitrile complexes of osmium and their reactions to give hydride, amine, and carbene complexes
Abstract
Uncharged and cationic isonitrile complexes of osmium of the types [OsCl2(RNC)2(PR13)2], [OsCl2(RNC)(PMe2Ph)3], [OsBr2(MeNC)4], [OsCl2(RNC)(PR13)3]ClO4, [OsCl2(RNC)2(PR13)2]ClO4, [OsCl(RNC)2(PR13)3]ClO4, and [Os(MeNC)6](ClO4)2(R = Me, Ph, p-MeOC6H4, or p-NO2C6H4; PR13= PMe2Ph, PEt2Ph, PBun2Ph, or PEt3) and the carbonyl–isonitrile complexes [OsCl2(CO)(PhNC)(PEt3)2], [OsCl(CO)(RNC)(PR13)3]ClO4(R = Me or Ph; PR13= PMe2Ph or PEt3) and [OsCl2(CO)(PhNC)(PEt3)2]ClO4 have been prepared. Some of the above compounds react with sodium borohydride or appropriate primary amines to give the compounds [OsHCl-(PhNC)(PMe2Ph)3] and [OsCl2(R2NH2)(PhNC)(PEt3)2](R2= Me or Et), the bis-carbene complex [Os(MeNC)4{C(NHMe)2}2](ClO4)2 and the tris-carbene complex [Os(MeNC)3{C(NHMe)2}3](ClO4)2. A few ruthenium complexes of the type [RuCl2(RNC)2(PR13)2](PR13= PMe2Ph, PPrn2Ph, or PBunPh) were also prepared and did not react with amines or alcohols. 1H N.m.r. and i.r. data are used to assign the configuration of the above compounds.
The reactivity towards nucleophiles of ligating isonitrile correlates with the magnitude of the increase of its N![[triple bond, length half m-dash]](https://www.rsc.org/images/entities/char_e007.gif)
C stretching frequency on co-ordination.
Please wait while we load your content...
