Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates

被引：171

作者：

Sartorel, Andrea ^{[2
]}

Miro, Pere ^{[1
]}

Salvadori, Enrico ^{[2
]}

Romain, Sophie ^{[1
]}

Carraro, Mauro ^{[2
]}

Scorrano, Gianfranco ^{[2
]}

Di Valentin, Marilena ^{[2
]}

Llobet, Antoni ^{[1
]}

Bo, Carles ^{[1
,3
]}

Bonchio, Marcella ^{[2
]}

机构：

[1] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain

[2] Univ Padua, ITM CNR, I-35131 Padua, Italy

[3] Univ Rovira & Virgili, Tarragona, Spain

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 44期

关键词：

OXYGEN-EVOLVING CATALYST; PHOTOSYSTEM-II; MOLECULAR DIOXYGEN; OXIDIZE WATER; BLUE DIMER; COMPLEXES; CHEMISTRY;

D O I：

10.1021/ja905067u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Converging UV-vis, EPR, rRaman, and DFT calculations highlight the evolution of [Ru-4(H2O)(4)(mu-O)(4)(mu-OH)(2)(gamma-SiW10O36)(2)](10-), 1, to high-valent intermediates. In analogy with the natural enzyme, five different oxidation states, generated from 1, have been found to power the catalytic cycle for water oxidation. A high electrophilic tetra ruthenium (V)-hydroxo species is envisaged as the competent intermediate, undergoing nucleophilic attack by an external water molecule as a key step in the formation of a new O-O bond under catalytic conditions.

引用

收藏

页码：16051 / +

页数：4

相关论文

共 26 条

[1] Mediator-assisted water oxidation by the ruthenium "blue dimer" cis,cis-[(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ [J].

Concepcion, Javier J. ;

Jurss, Jonah W. ;

Templeton, Joseph L. ;

Meyer, Thomas J. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2008, 105 (46) :17632-17635

[2] Preface on making oxygen [J].

Eisenberg, Richard ;

Gray, Harry B. .

INORGANIC CHEMISTRY, 2008, 47 (06) :1697-1699

[3] Architecture of the photosynthetic oxygen-evolving center [J].

Ferreira, KN ;

Iverson, TM ;

Maghlaoui, K ;

Barber, J ;

Iwata, S .

SCIENCE, 2004, 303 (5665) :1831-1838

[4] An all-inorganic, stable, and highly active tetraruthenium homogeneous catalyst for water oxidation [J].

Geletii, Yurii V. ;

Botar, Bogdan ;

Koegerler, Paul ;

Hillesheim, Daniel A. ;

Musaev, Djamaladdin G. ;

Hill, Craig L. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (21) :3896-3899

[5] Homogeneous Light-Driven Water Oxidation Catalyzed by a Tetraruthenium Complex with All Inorganic Ligands [J].

Geletii, Yurii V. ;

Huang, Zhuangqun ;

Hou, Yu ;

Musaev, Djamaladdin G. ;

Lian, Tianquan ;

Hill, Craig L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (22) :7522-+

[6] 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

[7] Powering the planet with solar fuel (vol 1, pg 7, 2009) [J].

Gray, Harry B. .

NATURE CHEMISTRY, 2009, 1 (01) :7-7

[8] In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+ [J].

Kanan, Matthew W. ;

Nocera, Daniel G. .

SCIENCE, 2008, 321 (5892) :1072-1075

[9] Synthesis and characterization of the keggin-type ruthenium-nitrido derivative [PW11O39{RuN}]4- and evidence of its electrophilic reactivity [J].

Lahootun, Vanina ;

Besson, Claire ;

Villanneau, Richard ;

Villain, Francoise ;

Chamoreau, Lise-Marie ;

Boubekeur, Kamal ;

Blanchard, Sebastien ;

Thouvenot, Rene ;

Proust, Anna .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (22) :7127-7135

[10] Mechanisms of water oxidation from the blue dimer to photosystem II [J].

Liu, Feng ;

Concepcion, Javier J. ;

Jurss, Jonah W. ;

Cardolaccia, Thomas ;

Templeton, Joseph L. ;

Meyer, Thomas J. .

INORGANIC CHEMISTRY, 2008, 47 (06) :1727-1752