Nucleophilic behaviour of the neutral complexes [M(ĈP)(S2CNMe2)] [M = Pd, Pt; ĈP = 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

Abstract

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.