Department of Chemistry, and Mathematical Modeling and Computational Science Center (LMCC), Katholieke Universiteit Leuven, B-3001-Leuven, Belgium.
Phys Chem Chem Phys. 2009 Nov 14;11(42):9703-9. doi: 10.1039/b911693a. Epub 2009 Sep 8.
The reactions of methane with different hydrides have been investigated using quantum chemical calculations (MP2 and CCSD(T) methods with the aug-cc-pVnZ one-electron functions extrapolated to the basis set limits). The hydrides of the elements of the second and third row, and also GaH(3), with an electronegativity smaller than the value of hydrogen (LiH, Li(2)H(2), BeH(2), NaH, MgH(2), BH(3), AlH(3), B(2)H(6), Al(2)H(6), SiH(4), PH(4) and GaH(3)) have been considered. Reactions of CH(4) with either BH(3) or LiH are characterized by the lowest energy barriers. Reactions using the known methylated derivatives of boranes with methane follow a similar mechanism. Calculated results strongly suggest the possible use of boranes as reagents in the reactions with methane to produce molecular hydrogen.
使用量子化学计算（MP2 和 CCSD(T)方法，使用 aug-cc-pVnZ 单电子函数外推到基组极限）研究了甲烷与不同氢化物的反应。考虑了第二和第三行元素的氢化物，以及电负性小于氢值的 GaH(3)（LiH、Li(2)H(2)、BeH(2)、NaH、MgH(2)、BH(3)、AlH(3)、B(2)H(6)、Al(2)H(6)、SiH(4)、PH(4)和 GaH(3)）。甲烷与 BH(3)或 LiH 的反应的特征在于最低的能垒。使用已知的硼烷甲基化衍生物与甲烷的反应遵循类似的机制。计算结果强烈表明硼烷作为试剂与甲烷反应生成氢气的可能性。
