Dataset Information

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 | 2021 Jan

REPOSITORIES: biostudies-literature

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

Pal Shrinwantu S Nozaki Kyoko K Vedernikov Andrei N AN Love Jennifer A JA

Chemical science 20210105 8

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 calcul ...[more]

PMID: 34164064

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Dataset Information

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

Publications

Reversible Pt<sup>II</sup>-CH<sub>3</sub> deuteration without methane loss: metal-ligand cooperation <i>vs.</i> ligand-assisted Pt<sup>II</sup>-protonation.

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