Theoretical and spectroscopic investigations of the bonding and reactivity of (RO)3M[triple bond]N molecules, where M = Cr, Mo, and W.

The electronic structures of the molecules ((t)BuO)(3)M[triple bond]N (M = Cr, Mo, W) have been investigated with gas phase photoelectron spectroscopy and density functional calculations. It is found that the alkoxide orbitals mix strongly with the M[triple bond]N triple bond orbitals and contribute substantially to the valence electronic structure. The first ionization of ((t)BuO)(3)Cr[triple bond]N is from an orbital of a(2)(C(3v)) symmetry that is oxygen based and contains no metal or nitrogen character by symmetry.