Flexible Platinum(0) Coordination to a Ditungsten Ethanediylidyne

Abstract

The lithiocarbyne [W(CLi)(CO) 2 (Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) reacts with [PtCl 2 -(L 2 )] (L 2 = 1,5-cyclo-octadiene,n orbornadiene) to furnish ditungsten ethanediylidyne complexes,[W 2 {m-C 2 Pt(L 2 )}(CO) 4 -(Tp*) 2 ], wherein at rigonal platinum(0) center unsymmetrically ligates one WCb ond in the solid state but rapidly shimmies between the two WCb onds in solution. The h 4dienes are displaced by monodentate CO or isocyanide ligands to provide derivatives where both W Cb onds coordinate to as ingle Pt 0 center,a ttended by significant distortion of the WCCW spine. Scheme 1. Valence bond localization of m-dicarbido complexes.Scheme 2. Ethanediylidyne synthesis and novel coordination modes.