caa a22 4500 605513279 CHVBK 20210128100659.0 cr unu---uuuuu 210128e20150501xx s 000 0 eng 10.1007/s00894-015-2678-1 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2678-1 A computational study on the insertion of CO2 into (PSiP)palladium allyl σ-bond [Elektronische Daten] [Qin Wang, Cai-Hong Guo, Ying Ren, Hai-Shun Wu] The insertion of CO2 into the (PSiP)palladium-allyl bond has been investigated using DFT. Three possible modes of CO2 insertion into (PSiP)Pd-allyl bond have been calculated, that is, direct 1.2-insertion mode, metallo-ene mode, and SE2 mode. The metallo-ene mode is the most favorable via the six-membered ring transition state. The results of calculations are consistent with the regioselectivity observed experimentally. The steric and electronic effects of different phosphine substituents have been evaluated by ONIOM and energy decomposition analysis (EDA) methods. For the phosphine substituents P(i-Pr)2 and PPh2, the contribution of electronic effect is greater than that of steric effect for the CO2 insertion into (PSiP)Pd-allyl bond; while for the phosphine substituent PMe2, the contribution of steric effect is slightly greater than that of electronic effect. Springer-Verlag Berlin Heidelberg, 2015 Carbon dioxide nationallicence DFT nationallicence ONIOM nationallicence Palladium nationallicence Regioselectivity nationallicence Wang Qin School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut Guo Cai-Hong School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut Ren Ying School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut Wu Hai-Shun School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-7 1610-2940 21:5<1 2015 21 894 https://doi.org/10.1007/s00894-015-2678-1 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/s00894-015-2678-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Wang Qin School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut NATIONALLICENCE 700 1- Guo Cai-Hong School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut NATIONALLICENCE 700 1- Ren Ying School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut NATIONALLICENCE 700 1- Wu Hai-Shun School of Chemistry and Materials Science, Shanxi Normal University, 041004, Linfen, People's Republic of China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-7 1610-2940 21:5<1 2015 21 894