Abstract
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 CH 3V(CO) 4DIARS, h 3-C 3H 5V(CO) 3DIARS and (OC) 5MnV(CO) 4DIARS which represent the first examples of alkyl, h 3-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.
Published Version
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