| Abstract
| - The electronic and steric factors that influence the conformational choice of the title complexes are theoretically analyzed. Structural correlations are proposed based on the computational results, which are consistent with the available experimental information.
- The binuclear complexes of d8 transition metal ions of the type [M2(μ-XR2)2L4] (where M = RhI, IrI, NiII, PdII,PtII, or AuIII; X = S, N, P, or As) appear in a variety of molecular conformations in which the coordinationplanes around the two metal atoms are sometimes coplanar, sometimes bent. For the bent compounds withasymmetric bridges, XR1R2, the substituents adopt different orientations relative to the metal framework and toeach other. Ab initio theoretical studies on the different conformers of 30 representative complexes, complementedwith a structural database analysis, have allowed the establishment of structural correlations in this family ofcompounds. The conformational choice results from a delicate balance of different interactions which arequalitatively analyzed, such as the changes in bond angles around the bridging atoms, the existence of weakmetal···metal bonding in the bent structures, and steric interactions involving the terminal ligands and thesubstituents at the bridging atoms.
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