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Phosphine σ-sydnonyl complexes of Ni, Pd, and Pt

3-R′-4-Bromosydnones 1 (R′ = Me) and 2 (R′ = Ph) react with complexes M(PR3)n (M = Ni, Pd, Pt) to form mononuclear phosphine σ-sydnonyl d8-complexes of trans-configuration MBr(3-R′-sydnon-4-yl)(PR3)2: 3, 4 (M = Ni, R′ = Ph); 5 (M = Pd, R′ = Me); 6a (M = Pd, R′ = Ph); 7 (M = Pt, R′ = Ph). In the reaction of bromosydnone 2 with Pd(PPh3)4, the cis-complex PdBr(3-Ph-sydnon-4-yl)(PPh3)2 (6b) is formed initially; 6b rearranges in solution to give trans-complex 6a. On heating in THF, complex 6a is converted into the binuclear [PdBr(3-phenylsydnon-4-yl)(PPh3)]2 complex (8). The reaction of 4-chloromercurio-3-phenylsydnone (10) with Ni(PEt3)4, Pt(PPh3)4, and Pt(PPh3)4 gives mononuclear NiCl(3-phenylsydnon-4-yl)(PEt3)2 complex (11), binuclear [PdCl(3-phenylsydnon-4-yl) (PPh3)]2 complex (14), and cis- and trans-bimetallic PtCl(3-phenylsydnon-4-ylmercurio)(PPh3)2 complexes 15a and 15b, respectively. UV irradiation of 15a and 15b in a benzene solution induces redox demercuration to yield the PtCl(3-phenylsydnon-4-ylcarbonyl)(PPh3)2 complex (16). In carbonylation of complexes 3, 6, and 7, CO insertion into the M-C bond occurred to form the corresponding acyl derivatives MBr(3-phenylsydnon-4-ylcarbonyl)(PR3)2 (17-19).