caa a22 4500 605487677 CHVBK 20210128100451.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1628-4 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1628-4 The ligand effect on the selective C-H versus C-C bond activation of propane by NiBr+: a theoretical study [Elektronische Daten] [Lianming Zhao, Qiuyue Ding, Wenbin Xu, Pengpeng Sang, Xiaoli He, Zemin Shi, Yuhua Chi, Xiaoqing Lu, Wenyue Guo] Density functional theory has been employed to investigate the ligand effect in the reaction of ligated NiBr+ with propane. Both initial C-H and C-C bond activation mechanisms for losses of HBr, H2, and CH4 are analyzed in terms of the topology of the potential energy surface. Losses of HBr and H2 involve three C-H activation mechanisms, that is, α,β-H, α,γ-H, and β,α-H abstractions, where the last β,α-H abstraction is the most favorable mechanism. Loss of CH4 involves initial C-C activation, but it is prevented by the high-energy barrier. When propane reacts with the open-shell ligated NiBr+, the ligand of Br in the initial C-H activation could direct abstract a H atom from propane substrate via a four-center transition state, without forming multi-σ-type bonding of Ni+, whereas the metal center in the initial C-C activation needs to experience an unfavorable three σ-type bonding (with Br, CH3, and CH2CH3), which explains why HBr and H2 are formed in the reaction of BrNi+/C3H8 and CH4 not. Springer-Verlag Berlin Heidelberg, 2015 Density functional theory nationallicence Ligand effect nationallicence Potential energy surface nationallicence Zhao Lianming College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Ding Qiuyue College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Xu Wenbin College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Sang Pengpeng College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut He Xiaoli College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Shi Zemin College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Chi Yuhua College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Lu Xiaoqing College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Guo Wenyue College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-13 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1628-4 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/s00214-015-1628-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zhao Lianming College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Ding Qiuyue College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Xu Wenbin College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Sang Pengpeng College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- He Xiaoli College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Shi Zemin College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Chi Yuhua College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Lu Xiaoqing College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 700 1- Guo Wenyue College of Science, China University of Petroleum, 266580, Qingdao, Shandong, People's Republic of China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-13 1432-881X 134:3<1 2015 134 214