Concerning the Spatial Nature of Metal-Thiolate π Bonding

References

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• For example, the electronic structures of bent metallocene complexes of the type Cp2MX2 have been modeled using the Extended Hückel24 and Fenske-Hall25,26a methods and have been experimentally investigated by single-crystal electron paramagnetic resonance spectroscopy26b, c and gas-phase photoelectron spectroscopy.25 The results of these studies indicate that the LUMO of the d0 and the HOMO of the d1 and d2 analogues is spatially localized in the plane containing the MX2 fragment and is normal to the plane that bisects the X-M-X angle. All of the bent metallocene compounds in Table I have a d0 electron configuration and are coordinatively unsaturated. Accordingly, the orientations observed for the thiolate ligands in these complexes indicate that the Spπ orbitals donate to the LUMO. In contrast, the thiolate ligands in bent metallocene compounds that have a d2 electron configuration and are coordinatively saturated are rotated 90° so as to minimize interaction between the metal-localized HOMO and the thiolate ligand Spπ orbitals.17
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• Hoffmann et al.28 have reported that the Extended Hückel method does not predict the conformation of CpMo(O)(C2(CF3)2)(SC6F5) observed in the solid-state as the electronically preferred conformation. However, we repeated these calculation and found that when the S-Mo-(C ≡ C centroid) angle is opened up to ca. 120°, an energy minimum is found very close to the geometry predicted by the simple-minded electronic model presented here.
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