Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic9907314
Title: Chemistry of thiocarboxylates: Synthesis and structures of neutral copper(I) thiocarboxylates with triphenylphosphine
Authors: Deivaraj, T.C. 
Lai, G.X.
Vittal, J.J. 
Issue Date: 6-Mar-2000
Citation: Deivaraj, T.C., Lai, G.X., Vittal, J.J. (2000-03-06). Chemistry of thiocarboxylates: Synthesis and structures of neutral copper(I) thiocarboxylates with triphenylphosphine. Inorganic Chemistry 39 (5) : 1028-1034. ScholarBank@NUS Repository. https://doi.org/10.1021/ic9907314
Abstract: The reactions of Na+ R{O}CS- (R = Me, Ph) with mixtures of CuCl and PPh3 in stoichiometric ratios yielded the compounds [Cu4(SC{O}Me)4(PPh3)4] (1), [Cu4(SC{O}Ph)4(PPh3)3] (2), [Cu2(SC{O}Me)2(PPh3)4] (3), [Cu-(SC{O}Ph)(PPh3)2] (4), and [Cu2(SC{O}Ph)2(PPh3)3] (5) quantitatively. Compound 2 was also obtained from mixtures of CuCl, PPh3, and NaSC{O}Ph in the ratio 1:1:1. The analogous thioacetate compound similar to 2 and the thiobenzoate analogue of 1 could not be obtained. Attempts to prepare the unsymmetrical dimer of a thioacetate compound similar to 5 gave a mixture of 1 and 3. The structures of 1-4 have been determined by single-crystal X-ray diffraction methods. Crystal data for 1: triclinic space group P1̄, a = 11.5844(3) Å, b = 13.2459(3) Å, c = 14.3433(3) Å, α = 64.019(1)°, β = 79,297(1)°, γ = 69.426(1)°, V = 1850.98(7) Å3, Z = 1, D(calcd) = 1.439 g·cm-3, Crystal data for 2·0.5CH2Cl2'H2O: triclinic space group P1̄, a = 12.4413(1) Å, b = 15.5443(1) Å, c = 20.4637(3) Å, α = 94.974(1)°, β = 95.976(1)°, γ = 100.450(1)°, V = 3848.09(7) Å3, Z = 2, D(calcd) = 1,416 g·cm-3. Single-crystal data for 3: monoclinic space group P21/n, a = 15.2746(2) Å, b = 23.2947(2) Å, c = 19.0518(3) Å, β = 96.713(1)°, V = 6732.5(2) Å3, Z = 4, D(calcd) = 1,309 g·cm-3. Crystal data for 4: triclinic space group P1̄, a = 10.2524(3) Å, b = 12.9826(4) Å, c = 14.5340(4) Å, α = 87.723(1)°, β = 75.322(1)°, γ = 75-978(1)°, V = 1815.14(9) Å3, Z = 2, D(calcd) = 1.327 g·cm-3. Compound 1, [(μ3-SC{O}Me-S)2(μ-SC{O}-Me-S)2(CuPPh3)4], is a tetramer with a distorted stepladder structure in which two copper atoms are trigonally coordinated and the other two are tetrahedrally coordinated. Two bonding modes, namely, μ3-S and μ2-S, were observed for the Me{O}CS- anion. The structure of 2 may be described as a highly distorted cubanoid structure and formulated as [(μ3-SC{O}Ph-S3)(μ3-SC{O}Ph-S2,O)3(Cu)(CuPPh3)3]. In 2, three copper atoms have tetrahedral coordination geometry and one copper atom is trigonally coordinated. Unprecedented bonding modes, namely, μ3-S, have been observed for the R{O}CS- anions, in 1 and 2 and μ3-S2,O in 2, Compound 3, [μ-SC{O}Me-S)(μ-SC{O}Me-S,O){Cu(PPh3)2}2] is a dimer with μ2-S and μ2-S,O bonding modes of Me{O}CS- ligands. Monomeric structure was found in 4 in which the copper atom has trigonal planar geometry with a very weak intramolecular interaction with O. Variable temperature 31P NMR studies in solution show the presence of various species in equilibria.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/93296
ISSN: 00201669
DOI: 10.1021/ic9907314
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