Groups 5 and 6 terminal hydrazido(2-) complexes: N(β) substituent effects on ligand-to-metal charge-transfer energies and oxidation states.

Brightly colored terminal hydrazido(2-) (dme)MCl(3)(NNR(2)) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl(4)(NNR(2)) complexes have been synthesized and characterized. Perturbing the electronic environment of the β (NR(2)) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the N(β) lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize N(β) in order to reduce the overlap between the Nb═N(α) π bond and the N(β) lone pair. For W complexes, increasing the energy of N(β) eventually leads to reduction from formally [W(VI)≡N-NR(2)] with a hydrazido(2-) ligand to [W(IV)═N═NR(2)] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives.