SYNTHESIS AND STRUCTURE OF 2 DINUCLEAR ANIONIC COMPLEXES, WITH PT(III)-PT(III) BONDS AND UNPRECEDENTED (C6F4O)(2-) OR (C6F4(OR)(2))(2-) (R=ME, ET) QUINONE-LIKE BRIDGING LIGANDS

A previously reported compound [NBu(4)] [Pt-2(mu-C6F5Cl)(mu-C6F5)(C6F5)(4)] (A) reacts with OH- or OR(-) (R = Me, Et) to give the dinuclear Pt(III) complexes [NBu(4)](2)[Pt-2(mu-C6F4O)(2)(C6F5)(4)] (1) or [NBu(4)](2)[Pt-2{mu-C6F4(OR)(2)}(2)-(C6F5)(4)] with R = Me (2) or Et (3). These three products contain pairs of quinone (C6F4O) or quinon-like (C6F4(OR)(2)) bridges and 1 and 2 have Pt-Pt single bonds with lengths of 2.570(1) and 2.584(1) Angstrom, respectively. The anions are strictly centrosymmetric and the central C2Pt(mu-C)(2)PtC2 cores have effective mmm symmetry. The mu-C6F4(OR)(2) ligands are readily hydrolyzed to give mu-C5F4O ligands. The crystallographic data are as follows. For 1, <P(1)over bar>, a = 12.055(2) Angstrom, b = 12.915(2) Angstrom, c = 13.055(2) Angstrom, alpha = 98.12(1)degrees, beta = 114.30(1)degrees, gamma = 86.02(1)degrees, V = 1833.7(5) Angstrom(3), Z = 1. For 2, P2(1)/c, a = 12.220(1) Angstrom, b = 21.552(2) Angstrom, c = 16.272(2) Angstrom, beta = 96.66(1)degrees, V = 4256(1) Angstrom(3), Z = 2.