Syntheses, Reactivities and Molecular Structures of Tungsten Complexes containing the Diphenylphosphinodithioformato Ligand

DOI: 10.1039/DT9950001305

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1305 - 1314 (1995)

Update date:2022-08-03

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Authors:

Yih, Kuang-Hway

Lin, Ying-Chih

Cheng, Ming-Chu

Wang, Yu

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Article abstract of DOI:10.1039/DT9950001305

Treatment of 1 with CS2 afforded 3 which was also synthesized from the reaction of with 2.The reactions of 3 with various alkyl halides gave the neutral complexes , and the reactions of 3 with acyl halides gave > (R = Me or Ph).Both alkylation and acylation reactions occur at the sulfur atom.Treatment of 3 with afforded <(OC)5W(μ-PPh2CS2)Re(CO)5> in which the two metal atoms were bridged by the PPh2CS2(1-) ligand.The reaction of 3 with (pip = piperidine) yielded and the dithiocarbamato tungsten complex .Complex 3 reacted with organic α,ω-diiodides (CH2I2, C2H4I2, C3H6I2), giving the phosphine bridged dinuclear complexes <2(μ-CH2)n> (n = 1-3), and only in the reaction of C3H6I2, was a mononuclear complex <>> seen as a minor product.Complex <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 .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) Angstroem, β = 102.02(2) deg, Z = 2, R = 0.062, R' = 0.073 based on 1180 reflections with I > 2 ?(I); 3, triclinic, space group P<*>, a = 10.688(3), b = 11.070(2), c = 12.785(2) Angstroem, α = 88.26(1), β = 81.87(2), γ = 74.081(17) deg, Z = 2, R = 0.028, R' = 0.025 based on 4557 reflections with I > 2?(I); 4a, triclinic, space group P<*>, a = 9.177(5), b = 9.403(3), c = 12.461(6) Angstroem, α = 90.00(3), β = 103.85(4), γ = 94.79(3) deg, Z = 2, R = 0.041, R' = 0.041 based on 2442 reflections with I > 2?(I).

Full text of DOI:10.1039/DT9950001305

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