N═N Bond Cleavage by Tantalum Hydride Complexes: Mechanistic Insights and Reactivity

The reaction of [TaCp^RX₄] (Cp^R = η⁵-C₅Me₅, η⁵-C₅H₄SiMe₃, η⁵-C₅HMe₄; X = Cl, Br) with SiH₃Ph resulted in the formation of the dinuclear hydride tantalum(IV) compounds [(TaCp^RX₂)₂(μ-H)₂], structurally identified by single-crystal X-ray analyses. These species react with azobenzene to give the mononuclear imide complex [TaCp^RX₂(NPh)] along with the release of molecular hydrogen. Analogous reactions between the [{Ta(η⁵-C₅Me₅)X₂}₂(μ-H)₂] derivatives and the cyclic diazo reagent benzo[c]cinnoline afford the biphenyl-bridged (phenylimido)tantalum complexes [{Ta(η⁵-C₅Me₅)X₂}₂(μ-NC₆H₄C₆H₄N)] along with the release of molecular hydrogen. When the compounds [(TaCp^RX₂)₂(μ-H)₂] (Cp^R = η⁵-C₅H₄SiMe₃, η⁵-C₅HMe₄; X = Cl, Br) were employed, we were able to trap the side-on-bound diazo derivatives [(TaCp^RX)₂{μ-(η²,η²-NC₆H₄C₆H₄N)}] (Cp^R = η⁵-C₅H₄SiMe₃, η⁵-C₅HMe₄; X = Cl, Br) as intermediates in the N═N bond cleavage process. DFT calculations provide insights into the N═N cleavage mechanism, in which the ditantalum(IV) fragment can promote two-electron reductions of the N═N bond at two different metal-metal bond splitting stages.