The reaction of cis-[Pt(PEt 3 ) 2 (OTf) 2 ] with 4-mercaptobenzoic acid (4-H 2 mba) in the presence of sodium methoxide yielded trans-[Pt(SC 6 H 4 COOH-4) 2 (PEt 3 ) 2 ] (1), the simple addition of 3-/4-mercaptobenzoic acid to cis-[Pt(PEt 3 ) 2 (OTf) 2 ] and cis-[M(_ PP) 2 (OTf) 2 ] gave the self-assembled complexes cis-[Pt(μ-SC 6 H 4 COOH-n)(PEt 3 ) 2 ] 2 (OTf) 2 [n = 3 (2), 4 (3)] and [M(μ-SC 6 H 4 COOH-n)(_ PP)] 2 (OTf) 2 [M/n/_ PP = Pd/3/dppe (4), Pd/4/ dppe (5), Pt/4/dppp (6); dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,2-bis(diphenylphosphino)propane], respectively, and the reactions of cis-[PtCl 2 (PR 3 ) 2 ] (R = Et, Ph) and [PtCl 2 (dppm)] with 3-/4-mercaptobenzoic acids in the pres-[a]