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

Chair of Physical Chemistry

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

66 Scopus citations

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.

Original language	English
Pages (from-to)	8200-8206
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	103
Issue number	41
DOIs	https://doi.org/10.1021/jp991665u
State	Published - 14 Oct 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.",

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doi = "10.1021/jp991665u",

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T1 - The Platinum Hydrido-Methyl Complex

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.

UR - https://www.scopus.com/pages/publications/0000134016

U2 - 10.1021/jp991665u

DO - 10.1021/jp991665u

M3 - Article

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SP - 8200

EP - 8206

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 41

ER -

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

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