Crystal and molecular structures of tri (o-tolyl)phosphinegold (I) O-alkyldithiocarbonates: o-tol3PAu(S2COR), R = iPr and CH2CH2OMe
Abstract
The crystal structures of the title compounds o-tol3PAu(S2COiPr), C25H28AuOPS2, and o-tol3PAu(S2COCH2CH2OMe), C25H28AuO2PS2, have been determined at room temperature. The colorless crystals of o-tol3PAu(S2COiPr) are monoclinic, space group P21/c, with unit cell dimensions a = 14.277(5) Å, b = 12.716(5) Å, c = 14.829(2) Å, β = 115.23(1)°, Z = 4 and Dx = 1.736 Mg m−3 and the pale-yellow crystals of o-tol3PAu(S2COCH2CH2OMe) are triclinic, space group P[unk], with dimensions a = 11.209(4) Å, b = 13.195(5) Å, c = 9.046(3) Å, α = 107.05(3)°, β = 91.78(3)° and γ = 74.40(3)°, Z = 2 and Dx = 1.761 Mg m−3. The structures were solved by direct-methods and each refined by a full-matrix least-squares procedure to final R = 0.041 (0.041) using 2887 (3841) reflections, respectively. The gold atom in each of the structures exists in a linear geometry defined by the S atom, derived from a monodentate xanthate ligand, and the phosphine P atom. The major difference between the two molecules is found in the orientation of the xanthate ligand. In the structure of o-tol3PAu(S2COiPr) the O atom is directed towards the Au atom, i.e. a ′S, O′ conformation, such that the Au … O separation is 2.892(7) Å, by contrast, in the structure of o-tol3PAu(S2COCH2CH2OMe) a close intramolecular Au … S contact of 3.347(3) Å is found; the ′S, S′ conformation. A variable-temperature multinuclear magnetic resonance (1H and 31P) study did not show the presence of both S, O and S, S conformations co-existing in solution for either of the compounds.
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