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Computational Comparative Mechanistic Study of C−E (E=C,N,O,S) Coupling Reactions through CO 2 Activation Mediated by Uranium(III) Complexes
Author(s) -
Ding Wanjian,
Liu Yanxiao,
Wang Dongqi
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804072
Subject(s) - chemistry , reactivity (psychology) , carboxylate , ligand (biochemistry) , nucleophile , iodide , stereochemistry , atom (system on chip) , medicinal chemistry , crystallography , inorganic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology , computer science , embedded system
A DFT mechanistic study is undertaken on the functionalization of CO 2 to form C−C, C−N, C−S, and C−O bonds promoted by trivalent uranium complexes (Tp*) 2 UR [Tp*=hydrotris(3,5‐dimethylpyrazolyl)‐borate ligand, R= −C≡ CPh (Cpda‐CC), −C≡CSiMe 3 (Cpda‐CSi), −NHPh (Cpda‐N), −SPh (Cpda‐S), and −OPh (Cpda‐O)]. These model systems are similar in view of their two‐step reaction mechanisms, that is, the insertion of CO 2 into the U−E (E=C, N, O, S) bond to form a [U‐ κ 1 ‐O 2 C] intermediate, followed by the reorientation of the carboxylate group to coordinate with the U atom in the κ 2 manner (Cpdb‐X, X=CC, CSi, N, S, O). However, the free energy barriers to the rate‐determining steps are substantially different, increasing in the order Cpda‐S