Oxalate-bridged dinuclear M2 units:: Dimers of dimers, cyclotetramers, and extended sheets (M = Mo, W, Tc, Ru, and Rh)

The electronic structures of D-4h-M-2(O2CH)(4) and the oxalate-bridged complexes D-2h-[(HCO2)(3)M-2](2)(mu-O2CCO2) and D-4h-(HCO2)(2)M-2](4)(mu-O2CCO2)(4) have been investigated by a symmetry analysis of their MM and oxalate-based frontier orbitals, as well as by electronic structure calculations on the model formate complexes (M = Mo and W {d(4)-d(4)}, Tc, Ru {d(6)-d(6)}, and Rh {d(7)-d(7)}. Significant changes in the ordering, interactions, and electronic occupation of the molecular orbitals (MOs) arise through both the progression from d(4) to d(7) metals and the change from second to third row transition metals. For M = Mo and W, the highest-occupied orbitals are 6 based, while the lowest-unoccupied orbitals are oxalate pi* based; for M = Tc, the highest-occupied orbitals are an energetically tight delta*-based set of MOs, while the lowest-unoccupied orbitals are MM-based pi*. For both Ru and Rh, the highest-occupied MOs are the MM pi* and delta*, respectively, while the lowest-unoccupied MOs, in both instances, are MM-based sigma*. With the exception of M = Ru, all of the complexes are closed shell. From the progression M-2 -> [M-2](2) -> [M-2](4), we can envision the nature of bandlike structures for a 2-dimensional square grid of formula [M-2(mu O2CCO2)infinity. Only for Mo and W oxalates should good electronic communication between MM centers generate a band of significant width to lead to metallic conductivity upon oxidation.