Croatica Chemica Acta, Vol. 56 No. 1, 1983.
Original scientific paper
MIND0/3 Study of Cyclopentadienylidene and Its Insertion into Molecular Hydrogen
Him-Tai Tsang
; Department of Chemistry, The Chinese University of Hong Kong Shatin, N. T., Hong Kong
Wai-Kee Li
; Department of Chemistry, The Chinese University of Hong Kong Shatin, N. T., Hong Kong
Abstract
The lowest singlet and triplet states of cyclopentadienylidene
(1) have been studied with the MIND0/3 method. It is found that ·
the ground state of 1 is a spin triplet, which is supported by
experimental finding and some previous calculations. The relationship
between the geometrical and electronic structures for
these states is also discussed.
In studying the least-motion and non-least-motion paths of
the hydrogen •insertion of 1, it is found that the latter is preferred
energetically. In addHion, as in the cases of other similar carbenehydrogen
reactions, the concerted non-least-motion path consists
of, in order, electrophilic and nucleophilic steps. However, for the
present reaction, in order to distinguish the two steps, the charges
on the hydrogens, rather than that on the carbenic center, should
be monitored.
Keywords
Hrčak ID:
194245
URI
Publication date:
15.4.1983.
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