Reversible PtII-CH3 deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted PtII-protonation.

Abstract

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield. The deuteration can be reversed by dissolution in CH3OH or CD3OH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal–ligand cooperative mechanism wherein DPK enables Pt–CH3 deuteration by allowing non-rate-limiting protonation of PtII by CD3OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of PtII, resulting in non-rate-limiting C–H(D) reductive coupling. Owing to its electron-poor nature, following complete deuteration, DPK can be dissociated from the PtII-centre, furnishing [(CD3)2PtII(μ-SMe2)]2 as the perdeutero analogue of [(CH3)2PtII(μ-SMe2)]2, a commonly used PtII-precursor.