Studies of oxalate-bridged MM quadruple bonds and their radical cations (M=Mo or W): on the matter of linkage isomers.

Electronic structure calculations employing density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been carried out on the model complexes {[(HCO2)3M2]2(mu-O2CCO2)}0/+(M=Mo or W) in D2h symmetry, where the oxalate bridge forms either five- or six-membered rings with the M(2) centres; the complexes are hereafter referred to as mu(5,5)0/+ and mu(6,6)0/+, respectively. The calculations predict that the neutral complexes should exist as the mu(5,5) linkage isomer, while the radical cations favour the mu(6,6) isomer by ca. 4-6 kJ mol-1. For the mu(5,5) isomers, the rotational barriers about the oxalate C-C bond have been calculated to be 15.9 and 27.2 kJ mol-1 for M=Mo and W, respectively. For the cationic mu(5,5)+ isomers the barrier is higher, being 36.8 and 50.6 kJ mol-1 for M=Mo and W, respectively. The calculated Raman and visible near-IR spectra for the mu(5,5)0/+ and mu(6,6)0/+ are compared with experimental data obtained for the {[(tBuCO2)3M2]2(mu-O2CCO2)}0/+ complexes, hereafter referred to as M4OXA0/+(M=Mo or W). The experimental data more closely correlate with that calculated for the mu(5,5)0/+ linkage isomers, and the 13C-NMR spectrum of the mixed metal complex Mo2W2OXA indicates the presence of the 5-membered oxalate-bridged species (J(CC)=100 Hz).