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A study of bond‐cleavage and bond‐formation processes in some simple metathesis reactions
Author(s) -
Sreedhara Rao V.,
Chandra A. K.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)63:6<1099::aid-qua3>3.0.co;2-s
Subject(s) - chemistry , bond cleavage , valence bond theory , generalized valence bond , bond order , metathesis , single bond , atom (system on chip) , computational chemistry , ab initio , bond length , crystallography , catalysis , molecule , organic chemistry , crystal structure , molecular orbital , polymerization , polymer , alkyl , computer science , embedded system
A few simple atom‐transfer reactions (i.e.,A˙+X−A→A−X+A˙) are studied by quantummechanical ab initio methods. Emphasis is given to the detailed analysis ofdensity matrices rather than to the energetics. Results reveal that duringthese reactions a small free valence always develops on the migrating atomat the transition state. The barriers in these reactions arise from thegreater extent of bond cleavage in the reactant than that of bond formationin the transition state. Analysis of bond orders estimated from bondlengths using Pauling's relation also leads to the fact that thebond‐cleavage process is more advanced than is the bond‐formation processin these reactions. © 1997 John Wiley & Sons, Inc. Int JQuant Chem 63 : 1099–1106, 1997