Gas-Phase Organometallic Chemistry: Chain-Length Effects

Article abstract of DOI:10.1021/ja00304a012

The gas-phase chemistry of Co(+) with a series of 1-chloro normal alkanes and alcohols with the alkyl chain length varying from three to eight carbon atoms is presented.In the case of chloroalkanes, as the chain length increases, metal ion insertion into internal C-C bonds becomes preferred over that into the C-Cl bond which is the dominant site of insertion for smaller chloroalkanes.The cobalt ion exhibits a much richer chemistry with alcohols by inserting into almost every skeletal C-C bond.A model suggesting metal-carbon atom interactions via cyclic intermediates leading to insertion into C-C bonds at specific distances from the initial site of complexation is used to account for the observed products for alcohols.This may also occur to a lesser extent for the chloroalkanes.The order of preference for the metal insertion is also deduced from these experiments and is contrasted with that of the corresponding alkanes.Trends in the relative probabilities for H shifts from alkyl groups and chloro- and hydroxyalkyl groups are discussed, and H shifts other than β-H shifts are also suggested.