摘要：

The molecular structures of copper(I) and silver(I) R 3P·M(SPR 2) 2N complexes (R=Ph; M=Cu, Ag), determined by single crystal X-ray crystallography, contain symmetrical M(SP) 2N six-membered rings in which both metal–sulfur bonds are similar in length, close to 2.2 Å (Cu) and 2.5 Å (Ag). The Au(I) compound is asymmetric, containing a linear Ph 3P–Au–S moiety, and a quasi-cyclic structure with two nonequivalent Au–S bonds (2.3 and 3.0 Å). Calculated structures are obtained for model compounds (R=H, CH 3) using PM3(d) semiempirical MO calculations, which are found to be inadequate for these types of structures. Ab initio DFT/B3LYP/LACVP ∗ for model compounds (R=H) accurately simulate the inorganic ring structures of all three compounds. A DFT optimization of the full phenyl-substituted gold complex yields a structure in good agreement with the X-ray data.

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