Nucleophilic behaviour of the neutral complexes [M(CP)-(S2CNMe2)] [M = Pd,Pt ; CP = CH2C6H4P(C6H4Me-o)(2)-kappa-C,P] towards Ag(I) and Au(I) compounds. Synthesis (M = Pd, Pt) and molecular structures (M = Pt) of polynuclearcomplexes 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)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 at oms are bridged by one S atom of the S2CNMe2 ligand and show a weak interac tion between them [Pt-Ag 2.875 (1) Angstrom]. Complexes A and B also react with AgClO4 in 1:1 molar ratio to give [M-2{CH2C6H4P(C6H4Me-o)(2)}(2)(S2CNM e2)(2)Ag{Ag(OClO3)}]ClO4 (M = Pt 5, Pd 6). The X-ray study of 5 revealed th at this compound crystallized as a mixture of [Pt-2{CH2C6H4P(C6H4Me-o)(2)}( 2)-(S2CNMe2)(2)Ag{Ag(OClO3)}]ClO4 and [Pt-2{CH2C6H4P(C6H4Me-o)(2)}(2)(S2CNM e2)(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 2.67 1 (3) Angstrom for [Pt-2{CH2C6H4P(C6H4Me-o)(2)}(2)(S2CNMe2)(2)Ag{Ag(OClO3)} ](+) and 2.752(3) Angstrom for [Pt-2{CH2C6H4P(C6H4Me-o)(2)}(2)(S2CNMe2)(2){ Ag(OH2)} {Ag(OClO3)}](+), both in the range found in other compounds with P t-Ag bonds. Compounds 5 and 6 react with PPh3 in 1:2 molar ratio to give co mpounds 1 and 2 respectively.