Isonitrile complexes of osmium and their reactions to give hydride, amine, and carbene complexes

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Abstract
Uncharged and cationic isonitrile complexes of osmium of the types [OsCl2(RNC)2(PR1 3)2], [OsCl2(RNC)(PMe2Ph)3], [OsBr2(MeNC)4], [OsCl2(RNC)(PR1 3)3]ClO4, [OsCl2(RNC)2(PR1 3)2]ClO4, [OsCl(RNC)2(PR1 3)3]ClO4, and [Os(MeNC)6](ClO4)2(R = Me, Ph, p-MeOC6H4, or p-NO2C6H4; PR1 3= PMe2Ph, PEt2Ph, PBun 2Ph, or PEt3) and the carbonyl–isonitrile complexes [OsCl2(CO)(PhNC)(PEt3)2], [OsCl(CO)(RNC)(PR1 3)3]ClO4(R = Me or Ph; PR1 3= 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(PR1 3)2](PR1 3= PMe2Ph, PPrn 2Ph, 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 NC stretching frequency on co-ordination.