Syntheses, reactivities and molecular structures of tungsten complexes containing the diphenylphosphinodithioformato ligand
Journal
Journal of the Chemical Society, Dalton Transactions
Journal Issue
8
Pages
1305-1313
Date Issued
1995
Author(s)
Abstract
Treatment of [NEt4][W(CO)5(PPh2)] 1 with CS2 afforded [NEt4][W(CO)5(PPh 2CS2)] 3 which was also synthesized from the reaction of [W(CO)5(MeCN)] with [NEt4][PPh2CS2] 2. The reactions of 3 with various alkyl halides gave the neutral complexes [W(CO)5{PPh2(CS2R)}] [R = Me(4a), Et, C 2H4OH, C3H5, CH2CN, C2H4CN or C3H6CN], and the reactions of 3 with acyl halides gave [W(CO)5{PPh2(CS 2COR)}] (R = Me or Ph). Both alkylation and acylation reactions occur at the sulfur atom. Treatment of 3 with [Re(CO)5Br] afforded [(OC)5W(μ-PPh2CS2)Re(CO)5] in which the two metal atoms were bridged by the PPh2CS2 - ligand. The reaction of 3 with [W(pip)2(CO)4] (pip = piperidine) yielded [W(CO)5(PPh2H)] and the dithiocarbamato tungsten complex [NEt4][W(CO)4(S 2CNC5H10)]. Complex 3 reacted with organic α,ω-diiodides (CH2I2, C2H 4I2, C3H6I2), giving the phosphine bridged dinuclear complexes [{W(CO)5(PPh2CS 2)}2(μ-CH2)n] (n = 1-3), and only in the reaction of C3H6I2, was a mononuclear complex {[W(CO)5{PPh2(CS2C3H 6I)}]} seen as a minor product. Complex [{W(CO)5(PPh 2CS2)}2(CO)2] was obtained from the reaction of 3 with oxalyl bromide in CH2Cl2. Thermolysis of 3 in tetrahydrofuran (thf) gave an anionic product identified as [NEt 4][W(CO)4(PPh2CS2)]. All of the complexes were identified by spectroscopic methods. The structures of complexes 2, 3, and 4a were confirmed by single-crystal X-ray diffraction analyses. Crystal data: 2, monoclinic, space group P21, a = 10.244(4), b = 9.877(4), c = 11.124(3) Å, β = 102.02(2)°, Z = 2, R = 0.062, R′ = 0.073 based on 1180 reflections with I > 2σ(I); 3, triclinic, space group P1, a = 10.688(3), b = 11.070(2), c = 12.785(2) Å, α = 88.26(1), β = 81.87(2), γ = 74.081(17)°, Z = 2, R = 0.028, R′ = 0.025 based on 4557 reflections with I > 2σ(I); 4a, triclinic, space group P1, a = 9.177(5), b = 9.403(3), c = 12.461(6) Å, α = 90.00(3), β = 103.85(4), γ = 94.79(3)°, Z = 2, R = 0.041, R′ = 0.041 based on 2442 reflections with I > 2σ(I).
SDGs
Type
journal article