Bis[1,2-bis(dimethylphosphino)ethane] dichlorotungsten(II) and its reactions. X-ray crystal structures of bis[1,2-bis(dimethylphosphino) ethane]tetrachlorotungsten(V) hexachloroantimonate(V) and bis{bis[1,2-bis(dimethylphosphino)ethane] tetrahydroaluminatohydridomolybdenum(II)}

Abstract

The reduction of WCl 4(THF) 2 by sodium naphthalenide in the presence of 1,2-bis(dimethylphosphino)ethane (DMPE) in tetrahydrofuran affords trans-WCl 2(DMPE) 2. Interaction of this complex with NaBPh 4 in MeCN gives [WCl(η 2-MeCN)(DMPE) 2]BPh 4 and with SbCl 5 the tungsten(V) complex [WCl 4(DMPE) 2]SbCl 6. The X-ray crystal structure of the latter shows the cation to have dodecahedral geometry with equatorial chlorine atoms. Interaction of trans-MCl 2(DMPE) 2 (M = Mo and W) with LiAlH 4 gives the hydrido aluminohydrides, [MH(AlH 4)(DMPE) 2] 2, and the X-ray crystal structure of the molybdenum compound has been determined. Methanolysis of the tungsten compound gives WH 4(DMPE) 2.