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Activation of Methane by Group 11 (Cu, Ag, Au) and Group 9 (Co, Ir) Transition Metal Atomic Anions
Tatsuya Chiba1, Joseph A Olaniyan2, Shiying Wang1
1Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States.
Abstract:
The interactions of transition metal atomic anions (Cu-, Ag-, Au-, Co-, Ir-) with methane were investigated via mass spectrometry, anion photoelectron spectroscopy, and quantum chemical calculations. Anion photoelectron spectra of the anionic metal atom-methane molecular complexes, [MCH4]-, combined with theoretical calculations showed that Cu- and Co- formed both chemisorption, HMCH3-, and physisorption (solvation), M-(CH4), complexes, while Ag- and Au- formed only physisorption complexes due to their high activation barriers. Also, the mass spectrum showed Ir- reacting with methane forming dehydrogenation products [IrCHn]- (n = 0-3) as well as the parent anion complex [IrCH4]-. While the anion photoelectron spectrum of [IrCH4]- showed the presence of the physisorption complex, Ir-(CH4), and evidence for the intermediates, H3IrCH- and H2IrCH2-, the theoretically predicted spectral band for the H4IrC- reaction product was outside of our experimental range.
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