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Reaction of CO 2 with a Vanadium(II) Aryl Oxide: Synergistic Activation of CO 2 /Oxo Groups towards H‐Atom Radical Abstraction
Author(s) -
Viasus Camilo J.,
Alderman Nicholas P.,
Gabidullin Bulat,
Gambarotta Sandro
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201805569
Subject(s) - chemistry , formate , deoxygenation , aryl , medicinal chemistry , vanadium , hydrogen atom abstraction , atom (system on chip) , residue (chemistry) , stereochemistry , radical , crystallography , inorganic chemistry , organic chemistry , catalysis , alkyl , computer science , embedded system
Abstract Treatment of divalent (ONNO)V(TMEDA) ( 1 ; ONNO=[2,4‐Me 2 ‐2‐(OH)C 6 H 2 CH 2 ] 2 N(CH 2 ) 2 NMe 2 ) with CO 2 afforded [(ONNO)V] 2 (μ‐OH)(μ‐formate) ( 2 ). Whereas the bridging hydroxo and formate groups both originated from CO 2 , the H atoms present on the two residues were obtained through H‐atom radical abstraction from the solvent. DFT calculations revealed an initially linear CO 2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so‐formed oxo group and an additional bridging CO 2 residue in promoting radical behavior.