Methylidene isocyanides, methyl isocyanides, and eta(2)-nitrile-pi-complexes are observed in the matrix IR spectra from reactions of Group 5 metals with acetonitrile isotopomers. The primary isocyanide products with no trace of cyanide complexes are consistent with the reaction path proposed in the analogous Zr study. The major products (CH2=Ta(H)NC, CH3-NbNC, eta Nb-2(NC)-CH3, and eta(2)-V(NC)-CH3) after codeposition and reaction of metal with CH3CN clearly show the increasing preference for the higher oxidation-state complex on going down the group column, and the subsequent photochemistry provides further information for molecular rearrangements. The Group 5 metal methylidene isocyanides exhibit more agostic distortion than the Zr counterparts and are comparable to the previously studied Group 5 metal methylidene hydrides and halides. The computed structures and observed frequencies indicate that the effects of metal conjugation (C=Ta-N=C:) are minor.