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Many binuclear nickel complexes have NiNi distances suggesting NiNi covalent bonds, including lantern‐type complexes with bridging bidentate ligands. This DFT study treats tetragonal, trigonal, and digonal lantern‐type complexes with the formamidinate, guanidinate, and formate ligands, besides some others. Formal bond orders (ranging from zero to two) are assigned to all the NiNi bonds on the basis of MO occupancy considerations. A VB‐based electron counting approach assigns plausible resonance structures to the dinickel cores. Model tetragonal complexes with the dimethylformamidinate and the dithioformate ligands have singlet ground states whose non‐covalently bonded NiNi distances are close to those in their experimentally known counterparts. Trigonal dinickel complexes are unknown, but are predicted to have quartet ground states with NiNi bonds of order 0.5. The model digonal complexes are predicted to have triplet ground states, but the predicted NiNi bond lengths are longer than those found in their experimentally known counterparts. This could owe to inadequate treatment of electron correlation by DFT in these short NiNi bonds with their multiconfigurational character. All the NiNi bond distances here are categorized into ranges according to the NiNi bond orders of 0, 0.5, 1, 1.5, and 2, no NiNi bonds of order higher than two being identified. The NiNi bonds of given order in these lantern‐type complexes are consistently shorter than the corresponding NiNi bonds in dinickel complexes having carbonyl ligands, attributable to the metalmetal bond lengthening effect of CO ligands.

Vanadium forms binuclear complexes with a variety of ligands often containing V≡V triple bonds. Many tetragonal divanadium paddlewheel complexes with bridging bidentate ligands have been experimentally characterized. This research exhaustively treats model tetragonal, trigonal, and digonal paddlewheel‐type divanadium complexes V₂L_x(L=formamidinate, guanidinate, and carboxylate;x=2, 3, 4), each in the three lowest‐energy spin states. The V−V formal bond orders are obtained from metal−metal MO diagrams for representative structures. A number of short V−V multiple bonds of order 3, 3.5, and 4 are found in these model complexes. The short V≡V triple bonds and singlet ground state predicted here for the model tetragonal complexes correspond well with the limited experimental results for the series of known tetragonal paddlewheels. Digonal divanadium lanterns with very short V−V quadruple bonds are predicted as interesting synthetic targets. The V−V bond distances are categorized into distinct ranges according to the formal bond order values from 0.5 to 4. These bond length ranges are compared with the ranges compiled for other divanadium complexes including carbonyl complexes.