Sulfinato Iron(III) Complex for Electrocatalytic Proton Reduction

被引：47

作者：

Cavell, Andrew C. ^{[1
]}

Hartley, Carolyn L. ^{[1
]}

Liu, Dan ^{[1
]}

Tribble, Connor S. ^{[1
]}

McNamara, William R. ^{[1
]}

机构：

[1] Coll William & Mary, Dept Chem, Williamsburg, VA 23185 USA

来源：

INORGANIC CHEMISTRY | 2015年 / 54卷 / 07期

基金：

美国国家科学基金会;

关键词：

HYDROGENASE ACTIVE-SITE; FE-ONLY HYDROGENASE; MOLECULAR ELECTROCATALYSTS; FUNCTIONAL MODELS; GENERATING HYDROGEN; LOW OVERPOTENTIALS; NITRILE HYDRATASE; CRYSTAL-STRUCTURE; EVOLUTION; COBALT;

D O I：

10.1021/ic5030394

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We report the first example of a sulfinato Fe(III) complex acting as a highly active electrocatalyst for proton reduction. The sulfinate binds to the metal through oxygen, resulting in a seven-membered chelate ring that is likely hemilabile during catalysis. Proton reduction occurs at -1.57 V versus Fc/Fc(+) in CH3CN with an i(c)/i(p) = 13 in CH3CN (k(obs) = 3300 s(-1)) and an overpotential of 800 mV. The catalysis is first order with respect to [catalyst] and second order with respect to [trifluoracetic acid]. An 11% increase in catalytic activity is observed in the presence of water, suggesting that sulfinate moieties are viable functional groups for aqueous proton reduction catalysts.

引用

页码：3325 / 3330

页数：6

共 50 条

[21] Selective electrocatalytic CO2 reduction by a polypyridyl-iron complex
Zee, David
Nippe, Michael
King, Amanda
Chang, Christopher
Long, Jeffrey
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2015, 250
[22] A pentacoordinated di-N-carboxamido-dithiolato-O-sulfinato-iron(III) complex related to the metal site of nitrile hydratase
Heinrich, L
Li, Y
Vaissermann, J
Chottard, G
Chottard, JC
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1999, 38 (23) : 3526 - 3528
[23] Reduction of maltolato complex of iron(III) by dithionite and glutathione.
Kazmi, SA
Amin, S
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2002, 224 : U660 - U661
[24] Electrocatalytic reduction of ROOH by iron porphyrins
Collman, JP
Kaplun, M
Sunderland, CJ
Boulatov, R
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (36) : 11166 - 11167
[25] Electrocatalytic reduction of no and nitrite by iron siderophores
Smith, SR
Thorp, HH
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1996, 211 : 169 - ANYL
[26] Proton-Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia
Rittle, Jonathan
Peters, Jonas C.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (40) : 12262 - 12265
[27] Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand-Based Proton and Electron Transfer
Thompson, Emily J.
Berben, Louise A.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (40) : 11642 - 11646
[28] Electrocatalytic proton reduction by a model for [NiFeSe] hydrogenases
Gezer, Gamze
Jimenez, Dinesh Duran
Siegler, Maxime A.
Bouwman, Elisabeth
DALTON TRANSACTIONS, 2017, 46 (23) : 7506 - 7514
[29] Photochemical desulfurization of a sulfinato-S-cobalt(III) complex. Formation of an organic peroxide complex
Akhter, FMD
Kojima, M
Nakajima, K
Yoshikawa, Y
CHEMISTRY LETTERS, 1996, (01) : 81 - 82
[30] Electrocatalytic O2 Reduction by an Organometallic Pd(III) Complex via a Binuclear Pd(III) Intermediate
Sinha, Soumalya
Mirica, Liviu M.
ACS CATALYSIS, 2021, 11 (09) : 5202 - 5211

← 1 2 3 4 5 →