Electronic States of 1,5-Cyclooctadiyne Radical Cation and of Related Systems: The electronic structure ofcis-bent carbon-carbon triple bonds

Autor:	Else Kloster-Jensen, Edgar Heilbronner, Jakob Wirz, Gerhard Bieri, Andreas Schmelzer
Rok vydání:	1974
Předmět:	Chemistry Organic Chemistry Bent molecular geometry Electronic structure Triple bond Biochemistry Catalysis Spectral line Inorganic Chemistry Crystallography chemistry.chemical_compound Radical ion Acetylene Computational chemistry Ionization Drug Discovery Physical and Theoretical Chemistry MINDO
Zdroj:	Helvetica Chimica Acta. 57:1265-1283
ISSN:	1522-2675 0018-019X
DOI:	10.1002/hlca.19740570504
Popis:	The photoelectron spectra of 1,5-cyclooctadiyne (2) and of 1,6-dithiacyclodeca-3,8-diyne (3) have been recorded. The first four (2) or six (3) PE. bands have been assigned as follows; in increasing order of ionization potentials: The relative sequence and the positions of the PE. bands are explained in terms of through-bond and through-space interactions between the basis π-orbitals and σ-orbitals of appropriate symmetry behaviour. An analysis of the PE. spectroscopic data for cyclooctyne (1) and for (2) indicates that a cis-bend of the acetylene moiety by θ < 20° leads to a split in energy of the in-plane and out-of-plane basis π-orbitals which is smaller than ∽ 0.2 eV. This is in agreement with the predictions derived from semiempirical models (MINDO/2, SPINDO) and qualitative orbital arguments. However, it is shown by using orbital localization procedures, that the rationales underlying the two semiempirical models differ significantly.
Databáze:	OpenAIRE
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