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β‐Fragmentation of Tertiary Alkoxyl Radicals: G3(MP2)‐RAD and Natural Bond Orbital Investigations
Author(s) -
Marque Sylvain R. A.,
Siri Didier
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100708
Subject(s) - lone pair , natural bond orbital , chemistry , radical , alkoxy group , fragmentation (computing) , homolysis , homo/lumo , bond cleavage , computational chemistry , stereochemistry , crystallography , molecule , organic chemistry , catalysis , computer science , density functional theory , alkyl , operating system
Amazing lone pair effect: G3 (MP2)‐RAD investigations combined with DFT calculations and NBO analysis shows that the β‐fragmentation of tertiary alkoxyl radicals R 1 R 2 YCO . (see picture) shows a banana bond at the TS (np,O→β‐LUMO) when Y bears a lone pair, in sharp contrast with the σ* CC →β‐LUMO interaction for the conventional homolytic CY bond cleavage.