Dynamics of the efficient cyclometalation of the undercoordinated organoplatinum complex [Pt(COD)(neoPh)](+) (neoPh=2-methyl-2-phenylpropyl)

Reaction of the organoplatinum complex [Pt(COD)(neoPh)Cl] (neoPh = (2-methyl-2-phenylpropyl)) with Ag(PF6) leads to the undercoordinated cationic complex [Pt(COD)(neoPh)](+) which rapidly and quantitatively rearranges to the complex [Pt(COD)(kappa(2)-neoPh)] through intramolecular cyclometalation. Detailed NMR spectroscopy and single crystal XRD reveal a doubly metalated neoPh ligand. In line with experimental observations, ab initio molecular dynamics simulations confirm that the cyclometalation reaction is exothermic and has a relatively low free energy barrier. In addition, the simulations provide detailed insight into the reaction mechanism, showing that an intermediate species exists in which the newly formed Pt-C bond coexists with a covalent Pt-H bond involving the leaving proton. The latter is found to eventually transfer onto an acetone solvent molecule