Reactions of methane with titanium atoms:: CH3TIH, CH2=TiH2, agostic bonding, and (CH3)2TiH2

被引：55

作者：

Andrews, L ^{[1
]}

Cho, HG ^{[1
]}

Wang, X ^{[1
]}

机构：

[1] Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA

来源：

INORGANIC CHEMISTRY | 2005年 / 44卷 / 13期

关键词：

D O I：

10.1021/ic0502574

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Laser-ablated titanium atoms react with methane to form the insertion product CHOH, which undergoes a reversible photochemical (x-H transfer to give the methylidene complex CH2=TiH2. On annealing a second methane activation occurs to produce (CH3)(2)TiH2. These molecules are identified from matrix infrared spectra by isotopic substitution (CH4, (CH4)-C-13, CD4, CH2D2) and comparison to DFT frequency calculations. The computed planar structure for singlet ground-state CH2=TiH2 shows CH2 distortion and evidence for agostic bonding (H-C-Ti, 91.4 degrees), which is supported by the spectra for CHD=TiHD.

引用

页码：4834 / 4842

页数：9

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