Binuclear Cobalt Paddlewheel-Type Complexes: Relating Metal-Metal Bond Lengths to Formal Bond Orders

Paddlewheel-type complexes are prominent among experimentally known binuclear cobalt complexes and incorporate substituted formamidinate, guanidinate, and carboxylate ligands in digonal, trigonal, and tetragonal arrays around the bimetallic core. Such complexes are modeled here by density functional theory using unsubstituted ligands, extending the whole set to incorporate a variety of metal oxidation states and spin multiplicities. The DFT results for ground state cobalt-cobalt bond lengths and ground state spin multiplicity of the model complexes are often quite close to the experimental results for the corresponding substituted complexes. The three series of complexes often exhibit parallel trends with regard to effects of change in the metal oxidation state and spin multiplicity. The formamidinate and guanidinate series show marked resemblances. The lowered symmetry in many model trigonal complexes implies that such deviations in the experimentally known congeners arise from the inherent electronic structure. For ground state species, the DFT results provide Co-Co bond orders (BOs) from MO occupancy considerations. Further, using a revised electron bookkeeping method, Co-Co formal bond order (fBO) values from 0.0 to 2.0 are assigned to all of the 85 complexes studied. The computed Co-Co bond lengths fall into distinct ranges according to the formal bond order values (from 0.5 to 2)