caa a22 4500 60551139X CHVBK 20210128100650.0 cr unu---uuuuu 210128e20150901xx s 000 0 eng 10.1007/s00894-015-2792-0 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2792-0 Mechanistic insights into small molecule activation induced by ligand cooperativity in PCcarbeneP nickel pincer complexes: a quantum chemistry study [Elektronische Daten] [Cheng-Cheng Liu, Qing-Lan Liu, Zun-Yi Wu, Ya-Cui Chen, Hu-Jun Xie, Qun-Fang Lei, Wen-Jun Fang] Mechanisms for the activation of water, ammonia, and other small molecules by the PCcarbeneP nickel pincer complex were studied computationally with the aid of density functional theory. The calculation results indicate that the strongly donating, nucleophilic carbene center can engage in a variety of heterolytic splitting of E−H (E=H, C, N, O) bonds, some of which are reversible. The cleavage of E−H bonds across the Ni=C bond represents a new mode of bond activation by ligand cooperativity in nickel pincer complex. On the basis of the calculations, we also demonstrate that reversible H2 activation across the Ir=C bond via the PCcarbeneP iridium pincer complex was observed in the experiments, while other E−H (E=C, N, O) bonds were not activated. Our calculations are in good agreement with experimental observations and could provide new insights into ligand cooperativity in nickel pincer complexes. Graphical Abstract Synopsis TOC Springer-Verlag Berlin Heidelberg, 2015 DFT calculations nationallicence Reaction mechanism nationallicence Nickel pincer complex nationallicence Ligand cooperativity nationallicence Activation nationallicence Liu Cheng-Cheng Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut Liu Qing-Lan Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut Wu Zun-Yi Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut Chen Ya-Cui Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut Xie Hu-Jun Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut Lei Qun-Fang Department of Chemistry, Zhejiang University, 310027, Hangzhou, China aut Fang Wen-Jun Department of Chemistry, Zhejiang University, 310027, Hangzhou, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-12 1610-2940 21:9<1 2015 21 894 https://doi.org/10.1007/s00894-015-2792-0 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/s00894-015-2792-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Liu Cheng-Cheng Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut NATIONALLICENCE 700 1- Liu Qing-Lan Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut NATIONALLICENCE 700 1- Wu Zun-Yi Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut NATIONALLICENCE 700 1- Chen Ya-Cui Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut NATIONALLICENCE 700 1- Xie Hu-Jun Department of Applied Chemistry, Zhejiang Gongshang University, 310018, Hangzhou, China aut NATIONALLICENCE 700 1- Lei Qun-Fang Department of Chemistry, Zhejiang University, 310027, Hangzhou, China aut NATIONALLICENCE 700 1- Fang Wen-Jun Department of Chemistry, Zhejiang University, 310027, Hangzhou, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-12 1610-2940 21:9<1 2015 21 894