How a [CoIV-O]2+ Fragment Oxidizes Water: Involvement of a Biradicaloid [CoII-(•O•)]2+ Species in Forming the O-O Bond
被引:46
作者:
Crandell, Douglas W.
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机构:
Indiana Univ, Dept Chem, Bloomington, IN 47405 USAIndiana Univ, Dept Chem, Bloomington, IN 47405 USA
Crandell, Douglas W.
[1
]
Ghosh, Soumya
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机构:
Indiana Univ, Dept Chem, Bloomington, IN 47405 USAIndiana Univ, Dept Chem, Bloomington, IN 47405 USA
Ghosh, Soumya
[1
]
Berlinguette, Curtis P.
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机构:
Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, CanadaIndiana Univ, Dept Chem, Bloomington, IN 47405 USA
Berlinguette, Curtis P.
[2
]
Baik, Mu-Hyun
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机构:
Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
Korea Univ, Dept Chem Mat, Jochiwon Eup 339700, Sejong Si, South KoreaIndiana Univ, Dept Chem, Bloomington, IN 47405 USA
Baik, Mu-Hyun
[1
,3
]
机构:
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
[2] Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada
[3] Korea Univ, Dept Chem Mat, Jochiwon Eup 339700, Sejong Si, South Korea
cobalt;
density functional theory;
photocatalysis;
solar fuels;
water oxidation;
DENSITY-FUNCTIONAL THEORY;
EFFECTIVE CORE POTENTIALS;
SOLVATION FREE-ENERGIES;
OXIDATION CATALYST;
MOLECULAR CALCULATIONS;
ELECTRONIC-STRUCTURE;
REDOX PROPERTIES;
RUTHENIUM COMPLEX;
OXYGEN EVOLUTION;
EFFICIENT;
D O I:
10.1002/cssc.201403024
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The mechanism of water oxidation performed by a recently discovered cobalt complex [Co(Py5)(OH2)](ClO4)(2) (1; Py5=2,6-(bis(bis-2-pyridyl)-methoxymethane)pyridine) was examined using quantum chemical models based on density functional theory. The computer models were first benchmarked against the experimental cyclic voltammetry data to identify the catalytically competent resting state of the catalyst, which was thought to contain a Co-IV-oxyl complex. The electronic structure calculations suggest that the low-spin doublet state is energetically most favorable, but the catalytically most active species is the intermediate-spin quartet complex that is almost isoenergetic with the doublet state. The electronic structure of the quartet state shows significant spin polarization on the terminal oxygen atom, which is consistent with an intramolecular electron transfer from the oxygen to the metal. Based on the calculated spin densities, the formally [Co-IV - O] can be viewed as a biradicaloid [Co-II(O)](2+), that is, a cobalt-oxene moiety. This electronic structure is reminiscent of many other systems where similar electronic patterns were proposed to be responsible for the oxidative reactivity. In this context, this first-row transition-metal system constitutes a logical extension, because the oxyl-radical character is maximized by using the more easily accessible high-spin configurations in which two half-filled Co-d pi orbitals can work in concert to maximize the oxyl-radical character to ultimately afford a new reactive intermediate that can be characterized as carrying a biradicaloid oxene moiety with a formal oxidation state of zero. This conceptual proposal for the catalytically active species provides a plausible rationale for the remarkable oxidative reactivity.
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Xu, Yunhua
;
Akermark, Torbjorn
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Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Akermark, Torbjorn
;
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机构:
Gyollai, Viktor
;
Zou, Dapeng
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机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Zou, Dapeng
;
Eriksson, Lars
论文数: 0引用数: 0
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机构:
Stockholm Univ, Dept Struct Chem, Arrhenius Lab, S-10691 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Eriksson, Lars
;
Duan, Lele
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机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Duan, Lele
;
Zhang, Rong
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机构:
Dalian Univ Technol, State Key Lab Fine Chem, KTH Joint Educ & Res Ctr Mol Devices, Dalian 116012, Peoples R ChinaStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Zhang, Rong
;
Akermark, Bjorn
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h-index: 0
机构:
Stockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Akermark, Bjorn
;
Sun, Licheng
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机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Xu, Yunhua
;
Akermark, Torbjorn
论文数: 0引用数: 0
h-index: 0
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Akermark, Torbjorn
;
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h-index:
机构:
Gyollai, Viktor
;
Zou, Dapeng
论文数: 0引用数: 0
h-index: 0
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Zou, Dapeng
;
Eriksson, Lars
论文数: 0引用数: 0
h-index: 0
机构:
Stockholm Univ, Dept Struct Chem, Arrhenius Lab, S-10691 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Eriksson, Lars
;
Duan, Lele
论文数: 0引用数: 0
h-index: 0
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Duan, Lele
;
Zhang, Rong
论文数: 0引用数: 0
h-index: 0
机构:
Dalian Univ Technol, State Key Lab Fine Chem, KTH Joint Educ & Res Ctr Mol Devices, Dalian 116012, Peoples R ChinaStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Zhang, Rong
;
Akermark, Bjorn
论文数: 0引用数: 0
h-index: 0
机构:
Stockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden
Akermark, Bjorn
;
Sun, Licheng
论文数: 0引用数: 0
h-index: 0
机构:
Royal Inst Technol KTH, Sch Chem Sci & Engn, S-10044 Stockholm, SwedenStockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden