The effects of -chloro substitution on the electronic structure of ClCr(+), ClMn(+), and ClFe(+) and resulting reactivity with small alkanes.

The exothermic reactions of chloro-substituted Cr(+), Mn(+) and Fe(+) in the gas phase with small hydrocarbons has been investigated in the ion trap of a Fourier transform mass spectrometer. Two types of reaction products are observed: those where the alkane simply attaches to the metal ion with displacement of a chlorine radical, and others where the C-C and/or C-H bonds of the alkane are activated leading to loss of neutral molecules of H(2) or a small alkane such as CH(4) from the metal ion complex. The reactivity displayed by ClCr(+) is particularly unusual.