Synthesis and reactivity of dinuclear complexes containing eta(2)-phenyl-metal interactions. Crystal structures of [NBu4][(C6F5)(3)Pt{mu-Ph2PCH2PPh(eta(2)-Ph)}Pt(C6F5)(2)] and [NBu4][(C6F5)(3)Pt(mu-dppm)Pt(C6F5)(2)(CO)]

摘要

Reaction between [NBu4][Pt(C6F5)(3)(dppm-kappa(1)P)] and cis-[M(C6X5)(2)(thf)(2)] (M = Pt, Pd; X = F, Cl; thf = tetrahydrofuran) leads to dinuclear derivatives with dppm Ligands bridging two metal centers: [NBu4][(C6F5)(3)Pt{mu-Ph2PCH2PPh(eta(2)-Ph)}M(C6X5)(2)] [X = F, M = Pt (1), M = Pd (2); X = Cl, M = Pt (3), M = Pd (4)]. The structural characterization of complex 1 by single-crystal X-ray diffraction (orthorhombic system, space group Fdd2, with a = 26.520(7) Angstrom, b = 83.69(3) Angstrom, c = 13.835(5) Angstrom, V = 30706(11) Angstrom(3), and Z = 16) reveals two square-planar platinum(II) fragments sharing a dppm ligand with a eta(2)-phenyl-platinum interaction between a phenyl ring of the dppm ligand and one platinum center. This weak eta(2)-phenyl-platinum interaction can be easily displaced by addition of ligands such as CO (giving complex 5), PPh3 (6), or p-toluidine (7). The structure of 5 was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group Pn, with a = 12.259(2) Angstrom, b = 16.375(3) Angstrom, c = 18.851(4) Angstrom, beta = 100.99(3)degrees, V = 3714.8 Angstrom(3), and Z = 2. The complex consists of two square-planar platinum(II) fragments with the dppm ligand acting as a conventional bridge. [References: 68]