TY - JOUR
T1 - Computational investigation of the reaction of NO with imine, silanimine, and its substituted derivatives
AU - Chen, Hui Lung
AU - Ho, Jia Jen
N1 - Funding Information:
Support for this research from the National Science Council of the Republic of China (NSC 94-2113-M-003-005) is gratefully acknowledged. We are also grateful to the National Center for High-Performance Computing where the Gaussian package and the computer time were provided.
PY - 2006/10/23
Y1 - 2006/10/23
N2 - The reaction mechanisms of HN{double bond, long}XH2 (X = C, Si) + NO were studied at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) level. The result indicated that the most favorable pathway of HN{double bond, long}CH2 + NO would lead to the formation of CH2N2 + OH with the calculated barrier of 44.41 kcal/mol, while in the reaction of HN{double bond, long}SiH2 + NO the most preferable pathway shifted to the production of H2SiOH + N2, a direct reduction of NO into a stable and nontoxic nitrogen molecule. The barrier of rate-determining step was calculated to be 18.90 kcal/mol, and it could be further decreased to 14.42 kcal/mol in the N-methyl substituted silanimine (CH3N{double bond, long}SiH2). It could be advantageous if it would act as a reactant in converting the reactive and toxic NO into a harmless N2 gas in several NO-producing combustion systems. The possible explanation to the differences between imine and silanimine toward the reaction with NO was provided.
AB - The reaction mechanisms of HN{double bond, long}XH2 (X = C, Si) + NO were studied at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) level. The result indicated that the most favorable pathway of HN{double bond, long}CH2 + NO would lead to the formation of CH2N2 + OH with the calculated barrier of 44.41 kcal/mol, while in the reaction of HN{double bond, long}SiH2 + NO the most preferable pathway shifted to the production of H2SiOH + N2, a direct reduction of NO into a stable and nontoxic nitrogen molecule. The barrier of rate-determining step was calculated to be 18.90 kcal/mol, and it could be further decreased to 14.42 kcal/mol in the N-methyl substituted silanimine (CH3N{double bond, long}SiH2). It could be advantageous if it would act as a reactant in converting the reactive and toxic NO into a harmless N2 gas in several NO-producing combustion systems. The possible explanation to the differences between imine and silanimine toward the reaction with NO was provided.
KW - Ab initio
KW - Donor-acceptor
KW - Imine
KW - NO
KW - Silanimine
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U2 - 10.1016/j.theochem.2006.06.022
DO - 10.1016/j.theochem.2006.06.022
M3 - Article
AN - SCOPUS:33747887726
VL - 772
SP - 93
EP - 102
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 1-3
ER -