Gas-Phase Organometallic Chemistry of Ni(1+), NiCO(1+), NiPF3(1+), and NiC5H5(1+) with Aromatic Compounds

Article abstract of DOI:10.1021/ja00184a007

The gas-phase chemistry of Ni(1+) and the monoligated nickel cations NiCO(1+), NiPF3(1+), and NiC5H5(1+) with a series of aromatic compounds is reported here.The phenyl group is largely unreactive and does not appear to prohibit the metal ion from interacting with other parts of these molecules.For some phenyl compounds, C6H5X, no reaction is observed for Ni(1+).When Ni(1+) does react, products such as NiC6H4(1+) and NiC5H5(1+) are formed-depending on the chemical composition of the attached functional group (X).Ni+ reacts with benzyl compounds by insertion into the C6H5CH2-X bond, frequently followed by charge transfer to form C7H7(1+) as a product.The Ni(1+) ion is observed to decarbonylate aromatic carbonyl compounds.When a single ligand is attached to the Ni(1+), changes in the chemistry are observed.In many cases, the reactivity decreases as the size of ligand increases, suggesting the importance of steric interactions even for these monoligated species.There are some exceptions, where NiC5H5(1+) is most reactive, even thought the cyclopentadienyl ligand is the largest.It is suggested that some charge transfer may occur in NiC5H5(1+), resulting in increased positive charge on the metal, loading to increased reactivity.