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http://hdl.handle.net/1942/9031
Title: | Theoretical study of alkali metal pyrrolides in comparison with nH-pyrrole | Authors: | Somers, KRF KRYACHKO, Eugene Ceulemans, A. |
Issue Date: | 2003 | Publisher: | AMER CHEMICAL SOC | Source: | JOURNAL OF PHYSICAL CHEMISTRY A, 107(28). p. 5427-5438 | Abstract: | The purpose of the present work is to demonstrate the remarkable difference between Li-pyrrolide, on one hand, and Na and K ones, on the other, viz., if the former exists as two conformers, a and 7 with a significant preference to the pi, at least in the gas phase, Na- and K-pyrrolides only establish the stable pi structure. A key factor of its higher stabilization is the formation of the M+delta-N-sigma ionic pair (M = Li, Na, and K) where the alkali metal atom behaves as a cation interacting with the pyrrole ring via a typical pi-cation interaction. The formation of alkali metal pyrrolides is related to the reactions of the N-H bond-breaking H abstraction and a further hydrogen "walk" along the pyrrole ring resulting in nH-pyrrole. Both reactions are thoroughly studied, and four novel pathways for the pyrolysis of pyrrole starting, by means of the 1,2 H migration, from pyrrolenine (2H-pyrrole) and exiting along the HCN-propyne channel, are proposed. | Notes: | Univ Louvain, Dept Chem, B-3001 Louvain, Belgium. | Document URI: | http://hdl.handle.net/1942/9031 | ISSN: | 1089-5639 | e-ISSN: | 1520-5215 | ISI #: | 000184084200009 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2004 |
Appears in Collections: | Research publications |
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