Reactivity and crystal structures of the first dithiocarbamate chromium(0) and dithiophosphate tungsten(0) complexes: crystal structures of [Et 4N][Cr(η 2-S 2CNC 5H 10)(CO) 4] and [Et 4N][W{η 2-S 2P(OEt) 2(CO) 4

Abstract

The structures of first dithiocarbamate chromium(0) complex [Et 4N][Cr(η 2-S 2CNC 5H 10)(CO) 4] ( 1) and the diethyldithiophosphate tungsten(0) complex [Et 4N][W{η 2-S 2P(OEt) 2(CO) 4] ( 2) have been determined by X-ray diffraction analyses. Crystal data for 1: space group, P2 1 with a=10.240(2) Å, b=12.705(4) Å, c=9.888(2) Å, β=117.26(2)°, V=1143.6(4) Å 3, and Z=2. The structure was refined to R=0.027 and R w=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) Å 3, and Z=4. The structure was refined to R=0.026 and R w=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(CH 3CN)(η 3-C 3H 5)(CO) 2{η 2-S 2P(OEt) 2}] ( 3) can be obtained from the reaction of [W(CH 3CN) 2(η 3-C 3H 5)(CO) 2Br] and (EtO) 2PS 2NH 4 in CH 3CN at room temperature but decomposed in the reaction of 2 with allyl bromide. Complex 3 reacted with dppe in CH 2Cl 2 at room temperature to give a mixture of complex [W(η 3-C 3H 5)(CO) 2{η 2-S 2P(OEt) 2}] 2(μ-dppe) ( 4) and [W(η 3-C 3H 5)(CO) 2{η 2-S 2P(OEt) 2(η 1-dppe)] ( 5).