Hydride abstraction of methylamine with Cu+(S-1) in the gas phase: A density functional theory study

作者：Lu Xiaoqing; Guo Wenyue^*; Zhao Lianming; Chen Xiangfeng; Fu Qingtao; Ma Yan

来源：Journal of Organometallic Chemistry, 2007, 692(17): 3796-3803.

DOI：10.1016/j.jorganchem.2007.05-030

• hydride abstraction
• methylamine
• transition metal ion
• density functional theory
• atoms in molecules theory
• natural bond orbital theory

The gas-phase hydride abstraction of methylamine with Cu+(S-1) is theoretically investigated by using density functional theory. ary points involved are fully optimized at both the B3LYP/6-311++G(d,p) and B3LYP/6-Geometries for all the station 31 1++G(3df,2p) levels and the reaction is analyzed in terms of the topology of potential energy surface. Approach of Cu towards methylamine could form either "classical" N or "nonclassical" Tl'-methyl-H attached complex with the former being the global minimum. Both complexes are found to be key intermediates for the hydride abstraction, which could transfer into each other via two parallel routes, i.e., concerted metal movement and stepwise C-H activation-rearrangement. A charge-transfer process is detected for the "nonclassical" complex converting to a precursor species (CuH-NH2CH2+), Which accounts for the final products by a nonreactive dissociation.

• 出版日期2007-8-1
• 单位中国石油大学（北京）