Di- and trinuclear phosphido-bridged platinum complexes. Crystal structures of [Pt{CH(2)=CHC(O)OMe}(PPh(3))(2)], trans-[Pt(2)(micro-PPh(2))(2)I(2)(PPh(3))(2)] and cis,cis,cis-[Pt(3)(mu-I)(2)(mu-PPh(2))(2)Cl(0.5)I(1.5)(PPh(3))(2)].

The readily available Pt(0) methyl acrylate complex [Pt{CH2CHC(O)OMe}(PPh3)2] (2) allows access to the known, mixed-valence trinuclear cluster [Pt3(mu-PPh2)3Ph(PPh3)2] (3) in 64% yield. Oxidation of 3 with 2 equivalents of I2 afforded the new trinuclear complex [Pt3(mu-I)2(mu-PPh2)2I2(PPh3)2] (4) whose molecular structure is similar to that of the related compound of empirical formula [Pt3(mu-I)2(mu-PPh2)2Cl0.5I1.5(PPh3)2] ( 5) which has been generated by oxidation of 3 with successively 1 equivalent of I2 and 1 equivalent of C6H5ICl2. In these complexes, the four halogen atoms lie on the same side of the almost aligned platinum atoms and the nearly square-planar coordination planes of the metal atoms adopt a japanese screen, chair-like conformation. The reaction of the dinuclear, metal-metal bonded Pt(I)-Pt(I) complex [Pt2(mu-PPh2)2(PPh3)2] with one equivalent of I2 afforded the Pt(II) complex [Pt2(mu-PPh2)2I2(PPh3)2] (6). The molecular structures of complexes 2 x CH2Cl2, [Pt3(mu-I)2(mu-PPh2)2(I1.3Cl0.7)(PPh3)2][Pt3(mu-I)2(mu-PPh2)2(I1.7Cl0.3)(PPh3)2] x C6H5Cl x 3CH2Cl2 (5A x 5B x C6H5Cl x 3CH2Cl2) and 6 have been established by single crystal X-ray diffraction studies.