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

Journal Article · Thu Oct 14 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp991665u· OSTI ID:20001147

Achatz, U; Beyer, M; Joos, S; Fox, B S; Niedner-Schatteburg, G; Bondybey, V E

Methane activation by transition metals has been a topic of growing interest during the past decade, due to economic interest in methane conversion and chemistry. Reactions of platinum-argon complexes Pt{sup +}Ar{sub m}, m = 1--6, with methane (CH{sub 4}) and methane-d{sub 4} (CD{sub 4}) were investigated by means of FT-ICR mass spectrometry and DFT calculations. Ligand exchange reactions are observed for Pt{sup +}Ar{sub 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{sup +}CH{sub 4} with CD{sub 4} and H{sub 2}O provide evidence for the inserted hydrido-methyl complex HPt{sup +}CH{sub 4} with CD{sub 4} (and the reverse reaction). This is attributed to the inability of the platinum cation to form more than three covalent bonds.

• Research Organization: Technische Univ. Muenchen, Garching (DE)
• OSTI ID: 20001147
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 41 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

03 NATURAL GAS
36 MATERIALS SCIENCE
ARGON
CHEMICAL REACTIONS
DEUTERIUM COMPOUNDS
MATHEMATICAL MODELS
METHANE
PLATINUM COMPLEXES
REACTION INTERMEDIATES