Two routes to bis(mu-diphenylphosphino)methane diplatinum halides bridged by sulfur monoxide

The new compounds Pt-2(mu-diphenylphosphinomethane)(2)(mu-SO)X-2, with X = Cl and I, have been prepared and characterized. One route was to use Pt-2(m u-dppm)(2)X-2 to trap the sulfur monoxide Liberated from decomposition of a sultine intermediate formed from the oxidation. of a thioketone sulfoxide with hydrogen peroxide, catalyzed by CH3ReO3 (MTO). The second and preferab le route consists of the oxidation of Pt-2(mu-dppm)(2)(mu-S)X-2 With hydrog en peroxide, catalyzed by CH3ReO3 (MTO). The X-ray structural analysis of P t-2(mu-dppm)(2)(mu-SO)Cl-2 showed that it has an "A-frame" structure in. wh ich the bridge sulfur atom has the geometry of a distorted trigonal bipyram id.