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On the mechanism of activation of coordinated olefins toward nucleophilic attack
Author(s) -
Cameron Alan D.,
Smith Vedene H.,
Baird Michael C.
Publication year - 1986
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.560300758
Subject(s) - ethylene , chemistry , nucleophile , olefin fiber , hydride , atomic orbital , molecular orbital , alkyl , computational chemistry , borohydride , photochemistry , medicinal chemistry , organic chemistry , molecule , catalysis , physics , electron , metal , nuclear physics
Attack by hydride sources such as the borohydride ion on complexes of the type [CpFe(CO) 2 (olefin)] + yields alkyl compounds of the CpFe(CO) 2 R. The mode of activation of the coordinated olefin ligands toward an incoming hydride nucleophile is investigated theoretically by utilizing extended Hückel and INDO methodologies. It was found that, of the two, the INDO approach yields reasonably accurate estimates of the energies of the ethylene frontier orbitals, and that activation (as measured by the extent of interaction between the hydride 1 s orbital and the coordinated ethylene) of the ethylene on coordination can occur because the ethylene π* orbital is considerably stabilized relative to the free ethylene π* orbital energy.