caa a22 4500 605488657 CHVBK 20210128100456.0 cr unu---uuuuu 210128e20151101xx s 000 0 eng 10.1007/s00214-015-1729-0 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1729-0 Mechanism of the sequential activation of two C-H bonds of a NHC N -methyl group on a triruthenium carbonyl cluster [Elektronische Daten] [Jing Yan, Zhe Han, Dongju Zhang, Chengbu Liu] Recent experimental studies on metal complexes of N-heterocyclic carbenes (NHCs) showed a few examples of the unique sequential activation of two C-H bonds of NHC N-methyl group on triruthenium carbonyl clusters. However, the corresponding theoretical calculations showed that the reactions are highly endergonic (>40kcal/mol) and involve very high barriers (up to ~80kcal/mol), failing to rationalize the experimental observations that the reactions were carried out under mild conditions (<100°C). The present work re-examines a representative example of the sequential activation of the two C-H bonds with the aid of density functional theory calculations. From the present results, the reaction is predicted to be endergonic by only 14.7kcal/mol with an overall barrier of 35.1kcal/mol, which is in good agreement with the experimental observations that the reaction smoothly proceeds under thermal reaction conditions and that the reversed transformation from the product to reactant occurs when carbon monoxide was gently bubbled into the reaction system at room temperature. Springer-Verlag Berlin Heidelberg, 2015 N -heterocyclic carbenes nationallicence Triruthenium carbonyl clusters nationallicence C-H bond activation nationallicence Density functional theory nationallicence Yan Jing Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut Han Zhe New Materials Institute of Shandong Academy of Sciences, 250014, Jinan, People's Republic of China aut Zhang Dongju Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut Liu Chengbu Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/11(2015-11-01), 1-7 1432-881X 134:11<1 2015 134 214 https://doi.org/10.1007/s00214-015-1729-0 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1729-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Yan Jing Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut NATIONALLICENCE 700 1- Han Zhe New Materials Institute of Shandong Academy of Sciences, 250014, Jinan, People's Republic of China aut NATIONALLICENCE 700 1- Zhang Dongju Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut NATIONALLICENCE 700 1- Liu Chengbu Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, 250100, Jinan, People's Republic of China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/11(2015-11-01), 1-7 1432-881X 134:11<1 2015 134 214