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

摘要

The structures of first dithiocarbarnate chromium(0) complex [Et4N][Cr(eta(2)-S2CNC5H10)(CO)(4)] (1) and the diethyldithiophosphate tungsten(0) complex [Et4N][W{eta(2)-S2P(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) Angstrom, b = 12.705(4) Angstrom, c = 9.888(2) Angstrom, beta = 117.26(2)degrees, beta = 1143.6(4) Angstrom(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) Angstrom, b = 16.220 (4) Angstrom, c = 11.417 (3) Angstrom, beta = 93.73 (3)degrees, V = 2412.3 (14) Angstrom(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) Angstrom in 1 indicates a considerable partial double bond character. The allyl dithiophosphate tungsten complex [W(CH3CN)(eta(3)-C3H5)(CO)(2){eta(2)-S2P (OEt)(2)}] (3) can be obtained from the reaction of [W(CH3CN)(2) (eta(3)-C3H5)(CO)(2)Br] and (EtO)(2)PS2NH4 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(eta(3)-C3H5)(CO)(2){eta(2)-S2P(OEt)(2)}](2)(mu-dppe) (4) and [W(eta(3)-C3H5)(CO)(2){eta(2)-S2P(OEt)(2)(eta(1)-dppe)] (5). (C) 2002 Elsevier Science B.V. All rights reserved. [References: 44]