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Reversible Pt^II-CH₃ deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted Pt^II-protonation.

ABSTRACT: Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(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)Pt^II(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 Pt^II by CD₃OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of Pt^II, 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 Pt^II-centre, furnishing [(CD₃)₂Pt^II(μ-SMe₂)]₂ as the perdeutero analogue of [(CH₃)₂Pt^II(μ-SMe₂)]₂, a commonly used Pt^II-precursor.

SUBMITTER: Pal S

PROVIDER: S-EPMC8179389 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Reversible Pt^II-CH₃ deuteration without methane loss: metal-ligand cooperation vs. ligand-assisted Pt^II-protonation.

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