Mechanism of water oxidation by the μ-oxo dimer [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+

被引：155

作者：

Binstead, RA ^{[1
]}

Chronister, CW ^{[1
]}

Ni, JF ^{[1
]}

Hartshorn, CM ^{[1
]}

Meyer, TJ ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2000年 / 122卷 / 35期

关键词：

D O I：

10.1021/ja993235n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The kinetics and mechanism of Ce-IV oxidation of the water oxidation catalyst [(bpy)(2)(H2O)Ru-III-ORuIII(OH2)(bpy)(2)](4+) (1, (RuORuIII)-O-III) have been investigated by UV-visible measurements with application of global analysis. The reaction proceeds by stepwise oxidation of (RuORuIII)-O-III to (RuORuV)-O-V with oxidation of (RuORuIII)-O-IV the slow step. (RuORuV)-O-V has been identified as an intermediate by the appearance of its ClO4- salt as a black suspension in concentrated solutions at 5 degrees C. It is the key intermediate in water oxidation. The mechanism may involve a bimolecular step and formation of a peroxo-bridged intermediate. Catalytic water oxidation is greatly retarded after just a few catalytic cycles because of anation induced by O-2 evolution.

引用

页码：8464 / 8473

页数：10

共 34 条

[1] REDOX AND SPECTRAL PROPERTIES OF THE 4-ELECTRON OXIDANT TRANS-[RU(TPY)(O)2(H2O)](CLO4)2 [J].

ADEYEMI, SA ;

DOVLETOGLOU, A ;

GUADALUPE, AR ;

MEYER, TJ .

INORGANIC CHEMISTRY, 1992, 31 (08) :1375-1383

[2] A NEW MODEL FOR THE OXYGEN-EVOLVING COMPLEX IN PHOTOSYNTHESIS - A TRINUCLEAR MU-3-OXO-MANGANESE(222) COMPLEX WHICH CONTAINS A MU-PEROXO GROUP [J].

BHULA, R ;

GAINSFORD, GJ ;

WEATHERBURN, DC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (22) :7550-7552

[3]

BOSSEK U, 1991, INORG BIOCHEM, V43, P371

[4]

CHRONISTER C, UNPUB

[5] Mechanism of water oxidation catalyzed by the mu-oxo dimer [(bpy)(2)(OH2)Ru(III)ORu(III)(OH2)(bpy)(2)](4+) [J].

Chronister, CW ;

Binstead, RA ;

Ni, JF ;

Meyer, TJ .

INORGANIC CHEMISTRY, 1997, 36 (18) :3814-3815

[6] ARTIFICIAL ANALOGS OF THE OXYGEN-EVOLVING COMPLEX IN PHOTOSYNTHESIS - THE OXO-BRIDGED RUTHENIUM DIMER 2,2'-BIPYRIDYL-4,4'-DICARBOXYLATE-2(H2O)RUIII-O-RUIII(H2O)L2 [J].

COMTE, P ;

NAZEERUDDIN, MK ;

ROTZINGER, FP ;

FRANK, AJ ;

GRATZEL, M .

JOURNAL OF MOLECULAR CATALYSIS, 1989, 52 (01) :63-84

[7] THE MANGANESE AND CALCIUM-IONS OF PHOTOSYNTHETIC OXYGEN EVOLUTION [J].

DEBUS, RJ .

BIOCHIMICA ET BIOPHYSICA ACTA, 1992, 1102 (03) :269-352

[8] SYNTHESIS AND REDOX PROPERTIES OF THE UNSYMMETRICAL, OXO-BRIDGED COMPLEX [(BPY)2(PY)RUIIIORUIII(H2O)(BPY)2]4+ [J].

DOPPELT, P ;

MEYER, TJ .

INORGANIC CHEMISTRY, 1987, 26 (13) :2027-2034

[9] CATALYTIC-OXIDATION OF WATER BY AN OXO-BRIDGED RUTHENIUM DIMER [J].

GERSTEN, SW ;

SAMUELS, GJ ;

MEYER, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (14) :4029-4030

[10] WATER OXIDATION BY [(BPY)2(O)RUVORUV(O)(BPY)2]4+ - AN OXYGEN-LABELING STUDY [J].

GESELOWITZ, D ;

MEYER, TJ .

INORGANIC CHEMISTRY, 1990, 29 (19) :3894-3896

← 1 2 3 4 →