Photosubstitution of V(CO)6- by o-phenylenebis(dimethylarsine) (DIARS) and 1,2-bis(dimethylphosphino)ethane (DMPE) provide highly reactive carbonylvanadate monoanions which have been protonated to give thermally stable seven coordinate carbonyl hydrides. The DIARS substituted anion, V(CO)4DIARS-, reacts with methyl iodide, allyl chloride and bromopentacarbonylmanganese to yield CH3V(CO)4DIARS, h3-C3H5V(CO)3DIARS and (OC)5MnV(CO)4DIARS which represent the first examples of alkyl, h3-allyl and mixed metal carbonyl derivatives of vanadium carbonyl. The chemical and spectral properties of these and related compounds are described. Controlled oxidation of V(CO)4DIARS- provides small yields of a very oxidatively unstable substance that appears to be monomeric V(CO)4DIARS. Reinvestigation of the reaction of vanadium hexacarbonyl and o-phenylenebis(dimethylarsine) in heptane has shown that a novel ionic species [V(CO)3(DIARS)2][V(CO)6], the first pnicogen derivative of the unknown V(CO)7+, is formed instead of the previously formulated neutral dimer [V(CO)4DIARS]2.