ISSN:
1434-1948
Keywords:
Density functional calculations
;
1,3-Diene-Fe(CO)3
;
Conformational analysis
;
Iron
;
Organometallic chemistry
;
Reactive intermediates
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A theoretical investigation of isoprene-Fe(CO)3 (2), (E)-1,3-pentadiene-Fe(CO)3 (3), (Z)-1,3-pentadiene-Fe(CO)3 (4), and reactive intermediates derived from these complexes was undertaken, employing the HF/DFT hybrid functional Becke3LYP, and the results are presented. Special emphasis is placed on cationic, anionic, and radical intermediates formally derived by abstraction of a hydride, a proton, or a hydrogen atom from the methyl group of the parent complexes. The geometry, energy, and electronic situation of the calculated species are discussed in the context of experimental facts. This leads to a better mechanistic understanding of the chemistry of acyclic butadiene-Fe(CO)3 complexes, provides insights into structural details of the intermediates involved, and allows the evaluation of possible resonance formulae. The calculation of transition states of isomerization (or racemization) processes even permits a quantitative description of energy profiles. In this way, the configurational stability of relevant cationic, anionic and radical intermediates can be estimated.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99146_s.pdf or from the author.
Additional Material:
15 Ill.
Type of Medium:
Electronic Resource
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