Abstract

Transmetallation studies with the phosphaethynolate ion, [OCP](-), have largely resulted in coordination according to classical Lewis acid-base theory. That is, for harder early transition metal ions, O-bound coordination has been observed, whereas in the case of softer late transition metal ions, P-bound coordination predominates. Herein, we report the use of a V(III) complex, namely [(nacnac) VCl(OAr)] (1) (nacnac(-) = [ArNC(CH3)](2)CH; Ar = 2,6-(Pr2C6H3)-Pr-i), to transmetallate [OCP](-) and bind via the P-atom as [(nacnac) V(OAr)(PCO)] (2), the first example of a 3d early transition metal that binds [OCP](-) via the P-atom. Full characterization studies of this molecule including HFEPR spectroscopy, SQuID measurements, and theoretical studies are presented.