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Titolo:
Density functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change
Autore:
Baik, MH; Ziegler, T; Schauer, CK;
Indirizzi:
Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA Univ N Carolina Chapel Hill NC USA 27599 Chem, Chapel Hill, NC 27599 USA Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada Univ Calgary CalgaryAB Canada T2N 1N4 Chem, Calgary, AB T2N 1N4, Canada
Titolo Testata:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
fascicolo: 38, volume: 122, anno: 2000,
pagine: 9143 - 9154
SICI:
0002-7863(20000927)122:38<9143:DFTSOR>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
ELECTRON-TRANSFER REACTIONS; METAL-METAL BOND; CORRECT ASYMPTOTIC-BEHAVIOR; SINGLE 2-ELECTRON PROCESS; TRANSITION-STATE METHOD; HIGH OXIDATION-STATES; GAS-PHASE IONIZATION; REDUCTION POTENTIALS; NEGATIVE-IONS; ORGANOMETALLIC ELECTROCHEMISTRY;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
110
Recensione:
Indirizzi per estratti:
Indirizzo: Schauer, CK Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA Univ N Carolina Chapel Hill NC USA 27599 l Hill, NC 27599 USA
Citazione:
M.H. Baik et al., "Density functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change", J AM CHEM S, 122(38), 2000, pp. 9143-9154

Abstract

The single-two-electron reduction for the Fe-Fe bonded dinuclear complexesFe-2(CO)(6)(mu(2)-PR2)(2) (R = CH3, 1-CH3; R = CF3, 1-CF3) is studied by electronic structure calculations based on density functional theory (DFT) methods. Several theoretical models are evaluated, including gas-phase models and models that include solvation (COSMO model) and/or countercations. The experimentally observed cleavage: of the Fe-Fe bond upon addition of electrons is reproduced in all calculations. The different theoretical models are evaluated by calculating the energy of the disproportionation reaction 2A(-) --> A + A(2-) using the energies of the complexes [1-R](0), [1-R](-), and [1-R](2-). As expected, gas-phase calculations poorly-model the experimental redox behavior, and the inclusion of salvation or: countercations is necessary to correctly: predict that the disproportionation reaction is energetically downhill. The distribution of the added electrons over the molecules and the charge distribution as a function of alkali:metal countercation (Li+, Na+, K+) are evaluated using the Hirshfeld charge analysis scheme. A qualitative correlation is found between the HOMO/LUMO energies Of the redox species and the calculated redox potentials.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 12/07/20 alle ore 02:34:48