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Borane–Lewis Base Complexes as Homolytic Hydrogen Atom Donors
Author(s) -
Hioe Johnny,
Karton Amir,
Martin Jan M. L.,
Zipse Hendrik
Publication year - 2010
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.200903395
Subject(s) - homolysis , borane , frustrated lewis pair , chemistry , lewis acids and bases , hydrogen atom , hydrogen , base (topology) , atom (system on chip) , photochemistry , catalysis , organic chemistry , radical , computer science , mathematical analysis , alkyl , mathematics , embedded system
Radical stabilization energies (RSE)s have been calculated for a variety of boryl radicals complexed to Lewis bases at the G3(MP2)‐RAD level of theory. These are referenced to the BH bond dissociation energy (BDE) in BH 3 determined at W4.3 level. High RSE values (and thus low BDE(BH) values) have been found for borane complexes of a variety of five‐ and six‐membered ring heterocycles. Variations of RSE values have been correlated with the strength of Lewis acid–Lewis base complex formation at the boryl radical stage. The analysis of charge‐ and spin‐density distributions shows that spin delocalization in the boryl radical complexes constitutes one of the mechanisms of radical stabilization.
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