Intramolecular versus intermolecular C-H activation reaction in the thermolysis of [Ru(Me)Cp*(PMe2Ph)2] (Cp*=n5-C5Me5): formation and crystallographic characterization of [Ru(Ph)Cp*(PMe2Ph)2]

Thermolysis of the ruthenium complex [Ru(Me)Cp*(PMe2Ph)2] (1) (Cp* = g5-C5Me5) in benzene gives methane and [Ru(Ph)Cp*(PMe2Ph)2] (2), which is converted slowly to [Ru(C6H4PMe2)Cp*(PMe2Ph)] (3) through the loss of benzene. 2 was structurally characterised by single-crystal X-ray diffraction experiments. DFT calculations were performed in order to understand the behaviour of the ruthenium complex 1 towards inter- or intra-molecular C–H bond activation reactions.