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Titolo:
Arene-mercury complexes stabilized aluminum and gallium chloride: Synthesis and structural characterization
Autore:
Borovik, AS; Bott, SG; Barron, AR;
Indirizzi:
Rice Univ, Dept Chem, Houston, TX 77005 USA Rice Univ Houston TX USA 77005 ice Univ, Dept Chem, Houston, TX 77005 USA Rice Univ, Ctr Nanoscale Sci & Technol, Houston, TX 77005 USA Rice Univ Houston TX USA 77005 scale Sci & Technol, Houston, TX 77005 USA Univ Houston, Dept Chem, Houston, TX 77204 USA Univ Houston Houston TX USA 77204 uston, Dept Chem, Houston, TX 77204 USA
Titolo Testata:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
fascicolo: 45, volume: 123, anno: 2001,
pagine: 11219 - 11228
SICI:
0002-7863(20011114)123:45<11219:ACSAAG>2.0.ZU;2-X
Fonte:
ISI
Lingua:
ENG
Soggetto:
MULTIDENTATE LEWIS-ACIDS; CROWDED ARYLOXIDE COMPOUNDS; SPIN QUADRUPOLAR NUCLEI; MIGRATION CO INSERTION; NMR-SPECTRA; CATIONIC ALUMINUM; PI-COMPLEXES; ACTIVATION; TOLUENE; ELECTROPHILES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
69
Recensione:
Indirizzi per estratti:
Indirizzo: Barron, AR Rice Univ, Dept Chem, Houston, TX 77005 USA Rice Univ Houston TX USA 77005 ept Chem, Houston, TX 77005 USA
Citazione:
A.S. Borovik et al., "Arene-mercury complexes stabilized aluminum and gallium chloride: Synthesis and structural characterization", J AM CHEM S, 123(45), 2001, pp. 11219-11228

Abstract

Reaction Of HgCl2 with 2 equiv Of MCl3 in an aromatic solvent yields Hg(arene)(2)(MCl4)(2) where, arene = C6H5Me, M = Al (1), Ga (2); arene = C6H5Et,M = At (3) and Ga (4); o-C6H4Me2, M = Al (5), Ga (6); C6H3-1,2,3-Me-3, M =Al (7) and Ga (8). The solid-state structures of compounds 1-5 and 7 have been determined by X-ray crystallography. In the solid state, compounds 1-4and 7 exist as neutral complexes in which two arenes are bound to the mercury, and the MCl3 groups are bound through bridging chlorides to the mercury; compound 5 exists as a cation-anion pair [Hg(o-C6H4Me2)(2)(AlCl4)][AlCl4]. However, in solution compounds 1-8 all exist as neutral complexes. The structures of Hg(arene)(2)(AlCl4)(2) and [Hg(arene)(2)(AlCl4)](+) have been determined by DFT calculations {B3LYP level} to facilitate the assignment of the C-13 CPMAS NMR spectra and are in good agreement with the X-ray diffraction structures of compounds 1 and 5. Reaction of HgCl2 with MCl3 in benzene, m-xylene, and p-xylene results in the formation of liquid clathrates whose spectroscopic characterization is consistent with ionic structures, [Hg(arene)(2)(MCl4)][MCl4]. The calculated energy difference between Hg(C6H5Me)(2)(AlCl4)(2) and [Hg(C6H5Me)(2)(AlCl4)][AlCl4] is discussed with respectto the structure of compound 5 in the solid state versus solution state and the proposed speciation in the liquid clathrates.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 23/09/20 alle ore 12:08:46