【摘 要】
：
The mechanisms of CO2 insertion into the U(Ⅲ)-N bond of M(LD)N”2(LD=2,6-iPr2-C6H3,N”=N(SiMe3)2)were investigated employing Gaussian09 package with B3PW91 functional of density functional theory.The re
【机 构】
：
Key Laboratory of Theoretical and Computational Photochemistry,Ministry of Education,College of Chem
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The mechanisms of CO2 insertion into the U(Ⅲ)-N bond of M(LD)N”2(LD=2,6-iPr2-C6H3,N”=N(SiMe3)2)were investigated employing Gaussian09 package with B3PW91 functional of density functional theory.The results support a three-step mechanism that CO2 inserts into the U(Ⅲ)-N bond directly,followed by SiMe3 migration and C-O bond broken to obtain the U(Ⅳ)complex.The reaction is thermodynamically favorable by 35.0 kcal/mol,and the free energy barrier to the rate-determining step is calculated to be 17.7 kcal/mol in vacuum and 18.in benzene.Another mechanism proposed by Arnold was also investigated in the present work,wher the free energy barrier to the rate-determinin stepwa estimated to be 72.0 kcal/mol,which is inhibitive under the experimental condition,thus less possible compared to the three-step mechanism mentioned above.
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