Reaction of LWI(RCN)(CO) with pyridine N-oxide results in the oxyfunctionalization of the kappa(2)N, C nitrile ligand and formation of the novel acylimido complexes LW{NC(O)R}I(CO) [L = hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Me, Et, Ph]. A derivative, LW{NC(O)Me}(SPh)(CO) (see illustration), exhibits a six-coordinate structure in which the orientation of the ligands is determined by pi-orbital overlap considerations.