Reduction pathway of end-on terminally coordinated dinitrogen. IV. Geometric, electronic, and vibrational structure of a W(IV) dialkylhydrazido complex and its two-electron-reduced derivative undergoing N-N cleavage upon protonation.

The molybdenum and tungsten dialkylhydrazido complexes [M(dppe)2 (NNC5H10)]2+ (M = Mo, W; compounds A(Mo) and A(W)) and their two-electron-reduced counterparts [M(dppe)2 (NNC5H10)] (compounds B(Mo) and B(W)) are characterized structurally and spectroscopically. The crystal structure of B(W) indicates a geometry between square pyramidal and trigonal bipyramidal with the NNC5H10 group in the apical position and in the trigonal plane of the complex, respectively. Temperature-dependent 31P NMR spectra of B(Mo) show that this geometry is present in solution as well. At room temperature, rapid Berry pseudorotation between the "axial" and "equatorial" ligand positions gives rise to a singlet in the 31P NMR spectrum. This exchange process is slowed at low temperature, leading to a doublet. The N-N distance of B(W) is 1.388 A, and the W-N distance is 1.781 A. Infrared and Raman spectroscopy applied to A(W), B(W), and their 15N isotopomers reveals extensive mixing between the N-N and W-N vibrations of the metal-N-N core with the modes of the piperidine ring. The N-N force constant of A(W) is determined to be 6.95 mdyn/A, which is close to the values of the Mo and W NNH2 complexes. In B(W), the N-N force constant decreases to 6.4 mdyn/A, which is between the values found for the Mo/W NNH3 and NNH2 complexes. This allows us to attribute N-N double bond character to A(W) and intermediate character between the double and single bonds for the N-N bond of B(W). These findings are supported by DFT calculations. More importantly, the HOMO of B(W) corresponds to a linear combination of the metal d(sigma) orbital with a ligand orbital having N-N sigma* character, inducing a weakening of the N-N bond. This contributes to the cleavage of the N-N bond taking place upon protonation of B(W) at the Nbeta atom of the NNC5H10 group.