Modulation of electronic and redox properties in phenolate-rich cobalt(III) complexes and their implications for catalytic proton reduction

Basu Debashis; Allard Marco M.; Xavier Fernando R.; Heeg Mary Jane; Schlegel H. Bernhard; Verani Claudio N.

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Modulation of electronic and redox properties in phenolate-rich cobalt(III) complexes and their implications for catalytic proton reduction

机译：富含酚盐的钴（III）配合物中电子和氧化还原特性的调节及其对催化质子还原的影响

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We investigate the redox, spectroscopy and catalytic reactivity of new cobalt(III) complexes based on phenolate-rich [N2O3] ligands. These complexes are described as [Co-III(L-X)MeOH], where X indicates the presence of chloro (1), bromo (2), iodo (3), or tert-butyl (4) substituents in the 3rd and 5th positions of each phenolate ring. These substituents modulate the Co(III) <- PheO(-) LMCT bands of the parent complexes with 1 (451) > 2 (453) > 3 (456) > 4 (468 nm) and the redox potentials involved with the Co(III)/Co(II) and ligand reduction and with the phenolate/phenoxyl oxidation processes. The influence of the substituents on the phenolate pendant arms was also observed on the kinetic parameters; 1 presented a rate constant of 1.0 x 10(-3) s(-1) whereas 4 showed a considerably slower rate (5.3 x 10(-5) s(-1)). Species 1 and 4 are electrocatalysts towards proton reduction in the presence of weak acid in acetonitrile. A TON of 10.8 was observed for 1 after 3 h of bulk electrolysis at -2.20 VFc/Fc+ using a mercury pool as the working electrode.

机译：我们研究了基于富含酚盐的[N2O3]配体的新型钴（III）配合物的氧化还原，光谱学和催化反应性。这些配合物描述为[Co-III（LX）MeOH]，其中X表示在第3和第5位上存在氯（1），溴（2），碘（3）或叔丁基（4）取代基每个酚盐环这些取代基以1（451）> 2（453）> 3（456）> 4（468 nm）调节母体配合物的Co（III）<-PheO（-）LMCT带，并且氧化还原电势与Co（ III）/ Co（II）和配体还原以及酚盐/苯氧基氧化过程。动力学参数也观察到了取代基对酚盐侧链的影响。 1的速率常数为1.0 x 10（-3）s（-1），而4的速率常数则慢得多（5.3 x 10（-5）s（-1））。物种1和4是在乙腈中存在弱酸时质子还原的电催化剂。使用汞池作为工作电极，在-2.20 VFc / Fc +下进行大量电解3小时后，观察到1的TON为10.8。

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《Dalton transactions: An international journal of inorganic chemistry》 |2015年第7期|共13页
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Basu Debashis; Allard Marco M.; Xavier Fernando R.; Heeg Mary Jane; Schlegel H. Bernhard; Verani Claudio N.;
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1. Modulation of electronic and redox properties in phenolate-rich cobalt(III) complexes and their implications for catalytic proton reduction [J] . Basu Debashis, Allard Marco M., Xavier Fernando R., Dalton transactions: An international journal of inorganic chemistry . 2015,第7期

机译：富含酚盐的钴（III）配合物中电子和氧化还原特性的调节及其对催化质子还原的影响
2. Synthesis, characterization, structure, redox property, antibacterial and catalytic activity of tridentate Schiff base cobalt(III), nickel(II) and palladium(II) complexes [J] . Pattanayak P., Pratihar J.L., Patra D., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2013,第Null期

机译：三齿席夫碱钴（III），镍（II）和钯（II）配合物的合成，表征，结构，氧化还原性质，抗菌和催化活性
3. Redox Properties and Catalytic Ability toward Electrochemical Proton Reduction of Sulfur-Bridged Trinuclear Mo3S4 Complexes Containing Acetate, Trifluoroacetate, and/or Dithiophosphate as Bridging Ligands [J] . Kawamoto Keisuke, Ichimura Akio, Hashimoto Hideki, Bulletin of the Chemical Society of Japan . 2015,第4期

机译：氧化氢，三氟乙酸酯和/或二硫代磷酸盐作为桥接配体的氧化硫 - 桥接三核MO3S4配合物的电化学质子络合物的氧化还原性能和催化能力
4. DIHYDROPTERIDINE/PTERIDINE AS A 2H+/2E- REDOX MEDIATOR FOR THE CATALYTIC REDUCTION OF CO2 TO METHANOL VIA HYDRIDE- PROTON TRANSFER [C] . Chern-Hooi Lim, Yu-Ching Kuo, Aaron M. Holder ACS National Meeting Exhibition . 2015

机译：二氢替昔胺/蝶呤作为2H + / 2E-氧化还原介体，用于通过氢化物转移催化减少CO 2至甲醇的介质
5. Developing artificial proteases and nucleases: Catalytic hydrolysis of unactivated amides, nitriles and phosphates. Part~I. Hydrolysis of phosphate esters promoted by cobalt(III) complexes. Part~II. Hydration of nitriles catalyzed by cobalt(III) complexes. Part~III. Hydrolysis of amides promoted by cobalt(III) complexes. [D] . Kim, Jung Hee. 1992

机译：开发人造蛋白酶和核酸酶：催化水解未活化的酰胺，腈和磷酸盐。第一部分钴（III）配合物促进的磷酸酯的水解。第二部分钴（III）配合物催化的腈水合。第三部分钴（III）配合物促进的酰胺水解。
6. Cobalt-dithiolene complexes for the photocatalytic and electrocatalytic reduction of protons in aqueous solutions [O] . William R. McNamara, Zhiji Han, Chih-Juo (Madeline) Yin, 2012

机译：钴-二硫烯配合物用于光催化和电催化还原水溶液中的质子
7. Catalytic proton reduction with transition metal complexes of the redox-active ligand bpy2PYMe [O] . Khnayzer Rony S., Nippe Micheal, Panetier Julien A., 2013

机译：氧化还原活性配体bpy2PYMe的过渡金属配合物催化质子还原
8. Ligand-Centered Electron-Transfer Redox Processes for Manganese, Iron, and Cobalt Complexes in Relation to Selected Catalytic Systems. [R] . Richert, S. A. 1989

机译：与选定的催化体系相关的锰，铁和钴配合物的配体中心电子转移氧化还原过程。

Modulation of electronic and redox properties in phenolate-rich cobalt(III) complexes and their implications for catalytic proton reduction

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