Synthesis and Structure of Two 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 [NBU4] [Ptz^-CeFsCl) (µ-CeFj) (CeFj)4] (A) reacts with OH- or OR- (R = Me, Et) to give the dinuclear Pt(III) complexes [NBu4] 2 [Pti^-C^O^CeFs)»] (1) or [NBu4] 2[Pt2{u-C6F4(OR)2j2-(C6F5)4] with R = Me (2) or Et (3). These three products contain pairs of quinone (C6F40) or quinon-like (C6F4(OR)2) and 1 and 2 have Pt-Pt single bonds with lengths of 2.570(1) and 2.584(1) A, respectively. The anions are strictly centrosymmetric and the central C2Pt^-C)2PtC2 cores have effective mmm symmetry. The µ-06 4( )2 ligands are readily hydrolyzed to give µ-CjF46 ligands. The crystallographic data are as follows. For 1, , a = 12.055(2) A, 6= 12.915(2) A, c = 13.055(2) A, a = 98.12(1)°, ß = 114.30(1)°, y = 86.02(1)°, V= 1833.7(5) A3 *****, Z = 1. For 2, P2,/c, a = 12.220(1) A, b = 21.552(2) A, c = 16.272(2) A, ß = 96.66(1)°, V= 4256(1) A3, Z = 2.