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Titolo:
Diruthenium complexes with hydrotris(1-pyrazolyl)borate face-capping ligands involving {Ru-2(mu-O or mu-OH)(mu-carboxylato)(2)} cores
Autore:
Tanase, T; Takeshita, N; Inoue, C; Kato, M; Yano, S; Sato, K;
Indirizzi:
Nara Womens Univ, Fac Sci, Dept Chem, Kitauoya Higashi, Nara 6308285, Japan Nara Womens Univ Kitauoya Higashi Nara Japan 6308285 Nara 6308285, Japan Tokyo Metropolitan Univ, Fac Engn, Dept Appl Chem, Tokyo 1920397, Japan Tokyo Metropolitan Univ Tokyo Japan 1920397 l Chem, Tokyo 1920397, Japan
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
fascicolo: 15, , anno: 2001,
pagine: 2293 - 2302
SICI:
1472-7773(2001):15<2293:DCWHFL>2.0.ZU;2-C
Fonte:
ISI
Lingua:
ENG
Soggetto:
ABSORPTION FINE-STRUCTURE; X-RAY STRUCTURE; MULTIPLE-SCATTERING CALCULATIONS; ELECTROCHEMICAL PROPERTIES; CRYSTAL-STRUCTURE; REDOX PROPERTIES; (MU-ALKOXO)BIS(MU-CARBOXYLATO)DIRUTHENIUM COMPLEXES; (MU-OXO)BIS(MU-CARBOXYLATO)DIRUTHENIUM COMPLEXES; BIOINORGANIC PERSPECTIVES; BRIDGING CARBOXYLATO;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
58
Recensione:
Indirizzi per estratti:
Indirizzo: Tanase, T Nara Womens Univ, Fac Sci, Dept Chem, Kitauoya Higashi, Nara 6308285, Japan Nara Womens Univ Kitauoya Higashi Nara Japan 6308285 285, Japan
Citazione:
T. Tanase et al., "Diruthenium complexes with hydrotris(1-pyrazolyl)borate face-capping ligands involving {Ru-2(mu-O or mu-OH)(mu-carboxylato)(2)} cores", J CHEM S DA, (15), 2001, pp. 2293-2302

Abstract

Reactions of [Ru-2(RCOO)(4)Cl] (R=Me, Ph) with K[HBpz(3)] (HBpz(3)(-)=hydrotris(1-pyrazolyl)borate) afforded the oxo-bridged diruthenium(III) complexes, [Ru-2(mu -O)(mu -RCOO)(2)(HBpz(3))(2)] (R=Me (1a), Ph (1b)) in moderateyields. Complexes 1 were converted by treatment with HPF6 into the hydroxo-bridged diruthenium(III) complexes, [Ru-2(mu -OH)(mu -RCOO)(2)(HBpz(3))(2)](PF6) (R=Me (2a), Ph (2b)), and by reaction with (NH4)(2)Ce(NO3)(6), to the oxo-bridged mixed-valence diruthenium(III, IV) complexes, [Ru-2(mu -O)(mu-RCOO)(2)(HBpz(3))(2)](PF6) (R=Me (3a), Ph (3b)). Complexes 1-3 were characterized by elemental analysis, IR, UV-Vis, and H-1 NMR spectroscopies, andX-ray absorption and crystallographic analyses (1a and 2a). Complex 1a consists of a {Ru-2(mu -oxo)(mu -carboxylato)(2)} core with two terminal face-capping HBpz(3)(-) ligands (Ru . . . Ru=3.2544(7) Angstrom). Protonation ofthe mu -oxo group of 1a expanded the Ru . . . Ru distance to 3.4490(9) Angstrom, which was elucidated by X-ray crystallography, and one-electron oxidation of 1a also increases this length to 3.38 Angstrom, determined by EXAFS analysis. These complexes interestingly showed, in cyclic voltammograms, a wide range of redox processes, [Ru-2(II)]<----> [(RuRuIII)-Ru-II]<----> [Ru-2(III)]<----> [(RuRuIV)-Ru-III]<----> [Ru-2(IV)], which are coupled withprotonation/deprotonation at the monoatom bridge. When complex 1b was reduced with sodium amalgam, the mononuclear ruthenium(II) complex [Ru(PhCOO)(HBpz(3))(CH3CN)(2)] (4b) was isolated and characterized by spectroscopic techniques and EXAFS analysis. Upon exposure to air or dioxygen, complex 4b readily regenerated the oxo-bridged dimer 1b, and the oxo atom was confirmed to be derived from dioxygen by an isotopically-labeled experiment. The present results demonstrate the versatile redox states of diruthenium centres terminally capped by HBpz(3)(-) ligands.

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Documento generato il 09/04/20 alle ore 20:06:36