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Density Functional Investigation of Reactive Intermediates Derived from Alkyne–Co 2 (CO) 6 Complexes
Author(s) -
Pfletschinger Anja,
Koch Wolfram,
Schmalz HansGünther
Publication year - 2001
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 - 10.1002/1521-3765(20011217)7:24<5325::aid-chem5325>3.0.co;2-s
Subject(s) - racemization , chemistry , cationic polymerization , density functional theory , alkyne , reactive intermediate , stereospecificity , computational chemistry , stereochemistry , polymer chemistry , catalysis , organic chemistry
By applying the hybrid density functional method B3LYP and a flexible all‐electron basis set, structures and energies of reactive intermediates derived from the 1‐butyne complex of Co 2 (CO) 6 ( 1 ) were calculated. In particular, the geometry, electronic distribution, and configurational stability of the cationic, radical, and anionic Co 2 (CO) 6 ‐complexed propargylic species were studied. The calculations revealed that the configurational barrier, that is, the racemization barrier for the antarafacial migration of the CHCH 3 group, is low (7.6 kcal mol −1 ) for the radical and is similar to the experimental value for the corresponding cation (ca. 10 kcal mol −1 ). However, a high racemization barrier (23.7 kcal mol −1 ) for the anionic intermediate suggests the possibility of stereospecific reactions involving Co 2 (CO) 6 ‐complexed propargylic anions.