The platinum hydride-methyl complex: A frozen reaction intermediate?

被引：62

作者：

Achatz, U ^{[1
]}

Beyer, M ^{[1
]}

Joos, S ^{[1
]}

Fox, BS ^{[1
]}

Niedner-Schatteburg, G ^{[1
]}

Bondybey, VE ^{[1
]}

机构：

[1] Tech Univ Munich, Inst Phys & Theoret Chem, D-85747 Garching, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 1999年 / 103卷 / 41期

关键词：

D O I：

10.1021/jp991665u

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Reactions of platinum-argon complexes Pt+Arm, m = 1-6, with methane (CH4) and methane-d(4) (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 hydride-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 land the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.

引用

页码：8200 / 8206

页数：7

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