The Platinum Hydrido-Methyl Complex: A Frozen Reaction Intermediate?

Uwe Achatz; Martin Beyer; Stefan Joos; Brigitte S. Fox; Gereon Niedner-Schatteburg; Vladimir E. Bondybey

doi:10.1021/jp991665u

The Platinum Hydrido-Methyl Complex: A Frozen Reaction Intermediate?

Uwe Achatz, Martin Beyer, Stefan Joos, Brigitte S. Fox, Gereon Niedner-Schatteburg, Vladimir E. Bondybey

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Technische Universität München

Publikation: Beitrag in Fachzeitschrift › Artikel › Begutachtung

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Abstract

Reactions of platinum-argon complexes Pt⁺Ar_m, m = 1-6, with methane (CH₄) and methane-d₄ (CD₄) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt⁺Ar_m, m = 2-6, in which up to four argon ligands are replaced by methane. In contrast the bare platinum ion and platinum solvated with one argon ligand lead to the formation of a platinum-carbene complex. Gibbs free enthalpies from ligand exchange reactions of Pt⁺CH₄ with CD₄ and H₂O provide evidence for the inserted hydrido-methyl complex HPt⁺CH₃ which is corroborated by high-level DFT calculations. No isotopic scrambling is observed for the reaction of Pt⁺CH₄ with CD₄ (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.

Originalsprache	Englisch
Seiten (von - bis)	8200-8206
Seitenumfang	7
Fachzeitschrift	Journal of Physical Chemistry A
Jahrgang	103
Ausgabenummer	41
DOIs	https://doi.org/10.1021/jp991665u
Publikationsstatus	Veröffentlicht - 14 Okt. 1999

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title = "The Platinum Hydrido-Methyl Complex: A Frozen Reaction Intermediate?",

abstract = "Reactions of platinum-argon complexes Pt+Arm, m = 1-6, with methane (CH4) and methane-d4 (CD4) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt+Arm, m = 2-6, in which up to four argon ligands are replaced by methane. In contrast the bare platinum ion and platinum solvated with one argon ligand lead to the formation of a platinum-carbene complex. Gibbs free enthalpies from ligand exchange reactions of Pt+CH4 with CD4 and H2O provide evidence for the inserted hydrido-methyl complex HPt+CH3 which is corroborated by high-level DFT calculations. No isotopic scrambling is observed for the reaction of Pt+CH4 with CD4 (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.",

author = "Uwe Achatz and Martin Beyer and Stefan Joos and Fox, {Brigitte S.} and Gereon Niedner-Schatteburg and Bondybey, {Vladimir E.}",

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T2 - A Frozen Reaction Intermediate?

AU - Achatz, Uwe

AU - Beyer, Martin

AU - Joos, Stefan

AU - Fox, Brigitte S.

AU - Niedner-Schatteburg, Gereon

AU - Bondybey, Vladimir E.

PY - 1999/10/14

Y1 - 1999/10/14

N2 - Reactions of platinum-argon complexes Pt+Arm, m = 1-6, with methane (CH4) and methane-d4 (CD4) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt+Arm, m = 2-6, in which up to four argon ligands are replaced by methane. In contrast the bare platinum ion and platinum solvated with one argon ligand lead to the formation of a platinum-carbene complex. Gibbs free enthalpies from ligand exchange reactions of Pt+CH4 with CD4 and H2O provide evidence for the inserted hydrido-methyl complex HPt+CH3 which is corroborated by high-level DFT calculations. No isotopic scrambling is observed for the reaction of Pt+CH4 with CD4 (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.

AB - Reactions of platinum-argon complexes Pt+Arm, m = 1-6, with methane (CH4) and methane-d4 (CD4) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt+Arm, m = 2-6, in which up to four argon ligands are replaced by methane. In contrast the bare platinum ion and platinum solvated with one argon ligand lead to the formation of a platinum-carbene complex. Gibbs free enthalpies from ligand exchange reactions of Pt+CH4 with CD4 and H2O provide evidence for the inserted hydrido-methyl complex HPt+CH3 which is corroborated by high-level DFT calculations. No isotopic scrambling is observed for the reaction of Pt+CH4 with CD4 (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.

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The Platinum Hydrido-Methyl Complex: A Frozen Reaction Intermediate?

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