Nucleophilic behaviour of the neutral complexes [M(C ̂ P)(S2CNMe2)] [M = Pd, Pt; C ̂ P = CH2C6H4P(C6H4Me-o)2-κ-C,P ] towards Ag(I) and Au(I) compounds. Synthesis (M = Pd, Pt) and molecular structures (M = Pt) of polynuclear complexes containing M–Ag and M–S bonds

The reactions between [M{CH2C6H4P(C6H4Me-o)2}(S2CNMe2)] (M = Pt A, Pd B) and [M′(OClO3)(PPh3)] (M′ = Ag, Au) in 1∶1 ratio yielded [M{CH2C6H4P(C6H4Me-o)2}(S2CNMe2)M′(PPh3)]ClO4 (M′ = Ag, M = Pt 1, Pd 2; M′ = Au, M = Pt 3, Pd 4). The molecular structure of 1 indicates that the Ag and Pt atoms are bridged by one S atom of the S2CNMe2 ligand and show a weak interaction between them [Pt–Ag 2.875 (1) Å]. Complexes A and B also react with AgClO4 in 1∶1 molar ratio to give [M2{CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag{Ag(OClO3)}]ClO4 (M = Pt 5, Pd 6). The X-ray study of 5 revealed that this compound crystallized as a mixture of [Pt2{CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag{Ag(OClO3 ) } ]ClO4 and [Pt2{CH2C6H4P(C6H4Me-o )2}2(S2CNMe2 )2{Ag(OH2)}{Ag(OClO3)}]ClO4 in 1∶1 molar ratio. In the two different cations only one Ag atom is bonded to Pt, with the Pt–Ag lengths being 2.671 (3) Å for [ Pt2{CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag{Ag(OClO3) } ]+ and 2.752(3) Å for [Pt2{CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2{Ag(OH2)}{Ag(OClO3)}]+, both in the range found in other compounds with Pt–Ag bonds. Compounds 5 and 6 react with PPh3 in 1∶2 molar ratio to give compounds 1 and 2 respectively.We thank the Dirección General de Enseñanza Superior (Spain) for financial support (Project PB95-0003-C02-01). One of us (A. M.) thanks the Spanish Ministerio de Educación y Ciencia for a F.P.U. (Becas en el extranjero) grant.Peer reviewe