10.1021/jp037010h.s001
Patrick W. Musch
Patrick W.
Musch
Daniel Scheidel
Daniel
Scheidel
Bernd Engels
Bernd
Engels
Comprehensive Model for the Electronic Structures of 1,2,4-Cyclohexatriene and Related
Compounds
American Chemical Society
2003
trend
chemical
interaction
ab initio methods show
Al
cyclic allenes
2003-12-18 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Comprehensive_Model_for_the_Electronic_Structures_of_1_2_4_Cyclohexatriene_and_Related_Compounds/3355939
To gain a better understanding of the chemistry of cyclic allenes, in the present work six-membered monocyclic
systems containing second- (B−O) and third-row elements (Al−S) of the periodic table of elements are
studied in detail, regarding the energetic order of the electronic states and the planarization energies, which
together determine their chemical behavior. The data obtained by high-level ab initio methods show that the
properties of the compounds strongly depend on the heteroatoms and can be related to trends in the periodic
table of elements. These trends in the series B to O and Al to S are rationalized by the degree of the interaction
between the various fragments and the interplay between this interaction and the strain in the allene moiety.
In addition, by applying the model to charged species, we reveal an unexpected link between the cyclic
allenes and the phenyl anion. Furthermore, our computations answer open questions about the chemical
properties of 1-aza-2,3-cyclohexadienes. Finally, we analyze how the various kinds of interaction influence
the chemistry of this important class of intermediates.