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Titolo:
Seven-coordinate d(0) and d(10) ions - Computational and experimental studies on tris(tropolonato)metal(III)-TOPO adducts
Autore:
Narbutt, J; Czerwinski, M; Krejzler, J;
Indirizzi:
Inst Nucl Chem & Technol, Dept Radiochem, PL-03195 Warsaw, Poland Inst Nucl Chem & Technol Warsaw Poland PL-03195 PL-03195 Warsaw, Poland Pedag Univ, Inst Chem, PL-42201 Czestochowa, Poland Pedag Univ Czestochowa Poland PL-42201 hem, PL-42201 Czestochowa, Poland
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 12, , anno: 2001,
pagine: 3187 - 3197
SICI:
1434-1948(200112):12<3187:SDADI->2.0.ZU;2-Y
Fonte:
ISI
Lingua:
ENG
Soggetto:
EFFECTIVE CORE POTENTIALS; TRIOCTYLPHOSPHINE OXIDE; AQUEOUS-SOLUTION; METAL-IONS; STRUCTURAL CHARACTERIZATION; MOLECULAR CALCULATIONS; CHELATE COMPLEXES; GALLIUM(III); EXTRACTION; CHEMISTRY;
Keywords:
chelates; thallium; yttrium; coordination chemistry; density-functional calculations; hypervalent compounds;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
50
Recensione:
Indirizzi per estratti:
Indirizzo: Narbutt, J Inst Nucl Chem & Technol, Dept Radiochem, Dorodna 16, PL-03195 Warsaw, Poland Inst Nucl Chem & Technol Dorodna 16 Warsaw Poland PL-03195 and
Citazione:
J. Narbutt et al., "Seven-coordinate d(0) and d(10) ions - Computational and experimental studies on tris(tropolonato)metal(III)-TOPO adducts", EUR J INORG, (12), 2001, pp. 3187-3197

Abstract

The stabilities of molecular adducts between tris(tropolonato)metal(III) chelates of some tripositive ions of Groups 3 and 13 and trioctylphosphane oxide (TOPO) were studied using both theoretical and experimental methods. Density-functional calculations were used to optimise the structure and characterise tris(tropolonates) of scandium and yttrium, a series of model chelates of gallium, indium, thallium, scandium, and yttrium, as well as the 1:1 adducts of these chelates with trimethylphosphane oxide, The calculated energy of adduct fori-nation decreased in the order: Y > Sc > Tl > In. Stability constants of the 1:1 (and some 1:2) TOPO adducts in solution, determined by synergistic solvent extraction of metal tropolonates, decreased in the same order. Both methods show that gallium does not increase its coordination number (CN) above six. The chelates of d(10) ions (CN 6) and their adducts (CN 7) are less stable than the corresponding d(0) species, because the former are hypervalent compounds with no higher-lying metal nd orbitals participating in bonding, while the latter have easily accessible vacant (n - 1)d orbitals. A significant distortion of the chelate structure makes theadducts of smaller ions less stable. Examination of bonding molecular orbitals in the adducts shows an unusual origin of the metal-TOPO bond, which may be due to a contribution from pi -bonding. Differences in some characteristics of indium and thallium. compounds can be explained by relativistic properties of thallium.

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Documento generato il 27/09/20 alle ore 07:10:59