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Titolo:
Binding interaction of the trimethylgermyl cation with acetophenones in the gas phase
Autore:
Mustanir; Mishima, M;
Indirizzi:
Kyushu Univ, Grad Sch Sci, Inst Fundamental Res Organ Chem, Higashi Ku, Fukuoka 8128581, Japan Kyushu Univ Fukuoka Japan 8128581 em, Higashi Ku, Fukuoka 8128581, Japan Kyushu Univ, Grad Sch Sci, Dept Chem & Phys Condensed Matter, Higashi Ku, Fukuoka 8128581, Japan Kyushu Univ Fukuoka Japan 8128581 er, Higashi Ku, Fukuoka 8128581, Japan
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
fascicolo: 5, , anno: 2001,
pagine: 798 - 803
SICI:
1472-779X(2001):5<798:BIOTTC>2.0.ZU;2-S
Fonte:
ISI
Lingua:
ENG
Soggetto:
PROTON AFFINITIES; SILYL CATION; TRIMETHYLSILYLIUM; BASICITIES; ASSOCIATION; RESONANCE; MOLECULES; (CH3)3SI+; CHEMISTRY; ENERGIES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
36
Recensione:
Indirizzi per estratti:
Indirizzo: Mishima, M Kyushu Univ, Grad Sch Sci, Inst Fundamental Res Organ Chem, Higashi Ku, Fukuoka 8128581, Japan Kyushu Univ Fukuoka Japan 8128581 Ku, Fukuoka 8128581, Japan
Citazione:
Mustanir e M. Mishima, "Binding interaction of the trimethylgermyl cation with acetophenones in the gas phase", J CHEM S P2, (5), 2001, pp. 798-803

Abstract

The gas-phase basicities towards the trimethylgermyl cation, GB(Me3Ge+), were determined for a series of acetophenones by measuring the equilibrium constants of trimethylgermyl cation transfer reactions. The effects of ring substituents on the Me3Ge+ basicities are excellently correlated in terms of the Yukawa-Tsuno equation, giving a rho value of -7.1 and an r(+) value of 0.71. These results suggest that the binding interaction of Me3Ge+ with the O atom of the carbonyl group of the acetophenones has a pronounced covalent character, resulting in the development of a positive charge at the benzylic carbon atom, although the delocalization of the positive charge into the benzene ring is slightly smaller than that for protonation. This feature of the adduct ion with Me3Ge+ resembles that for the Me3Si+ adduct ions and is consistent with results obtained by theoretical calculations at the DFT B3LYP/6-31+G* level of theory.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 10/12/19 alle ore 01:39:30