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Importance of frontier orbital interactions in addition reaction of water to disilene
Author(s) -
Takahashi Masae,
Veszprémi Tamás,
Kira Mitsuo
Publication year - 2001
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/qua.1321
Subject(s) - chemistry , ab initio , electrophile , nucleophile , molecular orbital , computational chemistry , transition state , molecule , organic chemistry , catalysis
Addition mechanisms of water to disilene were investigated in detail using the high level ab initio molecular orbital (MO) theory. We have found that the search for transition states by ab initio MO calculations combined with the frontier MO theory provides a good perspective view of the mechanisms of the reaction of disilenes and water. The initial electrophilic and nucleophilic interactions of the water with disilene give the corresponding weak complexes, C E and C N , which leads to the next nucleophilic and electrophilic attack of the water part, respectively. The latter pathway requires an antarafacial approach, while the former pathway proceeds via suprafacial addition. Whereas in the model disilene–water addition reaction, the pathway from C E is more favorable than the pathway from C N , the stereochemical ambiguity of the addition reactions found experimentally may be explained by the competition of the two pathways. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 192–197, 2001