Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2013-02-14

Coordination and bond activation in complexes of regioisomeric phenylpyridines with the nickel(II) chloride cation in the gas phase.

Alexandra Tsybizova, Lubomír Rulíšek, Detlef Schröder, Tibor András Rokob

Index: J. Phys. Chem. A 117(6) , 1171-80, (2013)

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Abstract

Electrospray ionization of dilute solutions of phenylpyridines (phpy) in the presence of nickel(II) chloride leads to gaseous ions of the type [Ni(phpy)(m)](2+) with m = 3-5 and [NiCl(phpy)(n)](+) with n = 1-3, which are characterized by various gas-phase experiments in combination with calculations using density functional theory. Of the regioisomeric phpy's, 2-phpy behaves drastically different compared to 3- and 4-phpy. Ion mobility mass spectrometry allows a differentiation of the gaseous ions and an elucidation of characteristic properties of the metal complexes. For 2-phpy, C-H bond activation in the [NiCl(phpy)(2)](+) complex is significant, whereas this route is almost suppressed for the corresponding complexes of 3- and 4-phpy and only occurs at elevated energies.