Methane activation by titanium monoxide molecules: a matrix isolation infrared spectroscopic and theoretical study

Guanjun Wang; Yu Gong; Mohua Chen; Mingfei Zhou

doi:10.1021/ja0604010

Methane activation by titanium monoxide molecules: a matrix isolation infrared spectroscopic and theoretical study

J Am Chem Soc. 2006 May 3;128(17):5974-80. doi: 10.1021/ja0604010.

Authors

Guanjun Wang¹, Yu Gong, Mohua Chen, Mingfei Zhou

Affiliation

¹ Department of Chemistry & Laser Chemistry Institute, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, People's Republic of China.

PMID: 16637666
DOI: 10.1021/ja0604010

Abstract

Reactions of titanium monoxides with methane have been investigated using matrix isolation infrared spectroscopy and theoretical calculations. Titanium derivatives of several simple oxyhydrocarbons have been prepared and identified. The titanium monoxide molecules prepared by laser evaporation of bulk TiO2 target reacted with methane to form the TiO(CH4) complex in solid argon, which was predicted to have C3v symmetry with the oxygen atom coordinated to one hydrogen atom of the methane molecule. The complex rearranged to the CH3Ti(O)H titano-acetaldehyde molecule upon visible (lambda > 500 nm) irradiation. The titano-acetaldehyde molecule sustained further photochemical rearrangement to the CH2Ti(H)OH titano-vinyl alcohol molecule, which was characterized to be a simple carbene complex involving agostic bonding. The CH2Ti(H)OH molecule reacted with a second methane to form the (CH3)2Ti(H)OH titano-isopropyl alcohol molecule spontaneously on annealing. The (CH3)2Ti(H)OH molecule also can be produced via UV photon-induced rearrangement of the CH3Ti(O)H(CH4) complex.