Reduction pathway of end-on coordinated dinitrogen. 3. Electronic structure and spectroscopic properties of...

The spectroscopic properties and electronic structure of the hydrazidium complexes [MF(NNH(3))(depe)(2)](BF(4))(2), M = Mo and W, are investigated (depe = 1,2-bis(diethylphosphino)ethane). Vibrational spectroscopic data for both compounds are evaluated with a quantum-chemistry-assisted normal coordinate analysis, giving an N-N force constant of 6.03 mdyn/A and metal-N force constants of 8.01 (Mo-N) and 7.31 mdyn/A (W-N), respectively. On the basis of these results and DFT calculations on a [MoF(NNH(3))(PH(3))(4)](2+) model system, the N-N bond order in these systems is 1 (single sigma bond) and metal-N bonding corresponds to a triple bond. The metal centers are assigned a +IV oxidation state (d(2) configuration) and the NNH(3) ligand is assigned a -1 formal charge which by sigma- and pi-donation to the metal is reduced to +0.48. The two metal-d electrons are located in the nonbonding (n) d(xy)() orbital. This bonding description is supported by the results of optical absorption spectroscopy showing the n --> (metal-ligand)pi transition at 536 nm (not observed in the tungsten compound) and the (metal-ligand)pi --> (metal-ligand)pi transition at 251 nm for the MoNNH(3) and at 237 nm for the WNNH(3) complex. The activation enthalpy for splitting of the N-N bond in these systems to generate NH(4)(+) is estimated to be larger than 40 kcal/mol. Hydrazidium complexes with diphosphine coligands are therefore inert with respect to N-N cleavage and thus represent the ultimate stage of N(2) reduction at six-coordinate d(6) metal centers in the absence of external reductants.