Square-planar imido complexes of cobalt: synthesis, reactivity and computational study.

Treatment of [Co(N)(PNP)] (PNP = anion of 2,5-bis(di--butylphosphinomethyl)pyrrole) with one equivalent of an aryl azide generates the four-coordinate imido complexes [Co(NAr)(PNP)] (Ar = mesityl, phenyl, or 4-Bu-phenyl). X-ray crystallographic analysis of the compounds shows an unusual square-planar geometry about cobalt with nearly linear imido units. In the presence of the hydrogen atom donor, TEMPOH, [Co(NPh)(PNP)] undergoes addition of the H atom to the imido nitrogen to generate the corresponding amido complex, [Co(NHPh)(PNP)], whose structure and composition were verified by independent synthesis.