Reactivity and crystal structures of the first dithiocarbamate chromium(0) and dithiophosphate tungsten(0) complexes: crystal structures of [Et4N][Cr(η2-S2CNC5H10)(CO)4] and [Et4N][W{η2-S2P(OEt)2(CO)4]

The structures of first dithiocarbamate chromium(0) complex [Et4N][Cr(η2-S2CNC5H10)(CO)4] (1) and the diethyldithiophosphate tungsten(0) complex [Et4N][W{η2-S2P(OEt)2(CO)4] (2) have been determined by X-ray diffraction analyses. Crystal data for 1: space group, P21 with a=10.240(2) Å, b=12.705(4) Å, c=9.888(2) Å, β=117.26(2)°, V=1143.6(4) Å3, and Z=2. The structure was refined to R=0.027 and Rw=0.028; Crystal data for 2: space group, C2/c with a=13.054 (6) Å, b=16.220 (4) Å, c=11.417 (3) Å, β=93.73 (3)°, V=2412.3 (14) Å3, and Z=4. The structure was refined to R=0.026 and Rw=0.019. The geometry around the metal atom in the anion of these two complexes is a distorted octahedron. The dithiocarbamato and diethyldithiophosphato ligands, respectively, coordinate to the Cr and W metal center through the two sulfur atoms. The short CN bond length of 1.335(4) Å in 1 indicates a considerable partial double bond character. The allyl dithiophosphate tungsten complex [W(CH3CN)(η3-C3H5)(CO)2{η2-S2P(OEt)2}] (3) can be obtained from the reaction of [W(CH3CN)2(η3-C3H5)(CO)2Br] and (EtO)2PS2NH4 in CH3CN at room temperature but decomposed in the reaction of 2 with allyl bromide. Complex 3 reacted with dppe in CH2Cl2 at room temperature to give a mixture of complex [W(η3-C3H5)(CO)2{η2-S2P(OEt)2}]2(μ-dppe) (4) and [W(η3-C3H5)(CO)2{η2-S2P(OEt)2(η1-dppe)] (5).