The reaction of Ph3AsCl2 with acetonitrile. Crystal structures of [Ph3AsNC(Me)C(AsPh3)CN]Cl-+(-) and of the palladium molecular complex [Ph3AsNC(Me)C(AsPh3)CN-PdCl3]

In the presence of potassium hydride the reaction of Ph3AsCl2 with acetonit rile leads to [Ph3AsNC(Me) . C(AsPh3)CN]Cl-+(-) (1), which is characterized by its infrared spectrum and by a crystal structure analysis. 1 can be exp lained as an insertion reaction of acetonitrile into an ylidic As-C bond of the primarily formed [(Ph3As)(2)CCN]Cl. 1: Space group P (1) over bar, Z = 2, lattice dimensions at -70 degrees C: a = 991.9(1), b = 1255.2(1), c = 1381.3(1) pm, alpha = 81.64(1)degrees, bet a = 80.12(1)degrees, gamma = 78.17(1)degrees; R-1 = 0.051. 1 reacts with pa lladium(II) chloride to give the molecular complex [Ph3AsNC(Me)C(AsPh3)CN-P dCl3] (2) with zwitterionic structure. The fragment [PdCl3-] is terminally bonded at the nitrogen atom of the CCN group of the cation of 1 in a linear arrangement CCNPd. 2 . CH3CN: Space group P2(1), Z = 2, lattice dimensions at -90 degrees C: a = 1079.2(1), b = 1261.5(1), c = 1560.9(1) pm; beta = 110.20(1)degrees; R-1 = 0.0283.