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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(CH 3 )] 2 CH; Ar = 2,6- i Pr 2 C 6 H 3 ), 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.

Finding a soft spot for vanadium: a P-bound OCP ligand