Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)(3)] complexes

Agarwal Jay; Stanton Charles J. III; Shaw Travis W.; Vandezande Jonathon E.; Majetich George F.; Bocarsly Andrew B.; Schaefer Henry F. III

首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)(3)] complexes

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Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)(3)] complexes

机译：探索轴向配体取代（X = Br，NCS，CN）对[MnX（N-C）（CO）（3）]配合物的光分解和电化学活性的影响

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The synthesis, electrochemical activity, and relative photodecomposition rate is reported for four new Mn(I) N-heterocyclic carbene complexes: [MnX(N-ethyl-N'-2-pyridylimidazol-2-ylidine)(CO)(3)] (X = Br, NCS, CN) and [MnCN(N-ethyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)(3)]. All compounds display an electrocatalytic current enhancement under CO2 at the potential of the first reduction, which ranges from -1.53 V to -1.96 V versus the saturated calomel electrode. Catalytic CO production is observed for all species during four-hour preparative-scale electrolysis, but substantial H-2 is detected in compounds where X is not Br. All species eventually decompose under both 350 nm and 420 nm light, but cyanide substituted complexes (X = CN) last significantly longer (up to 5x) under 420 nm light as a result of a blue-shifted MLCT band.

机译：报告了四种新的Mn（I）N-杂环卡宾配合物的合成，电化学活性和相对光解速率：[MnX（N-乙基-N'-2-吡啶基咪唑-2-基吡啶）（CO）（3）] （X ＝ Br，NCS，CN）和[MnCN（N-乙基-N′-2-吡啶基苯并咪唑-2-基吡啶）（CO）（3）]。与饱和甘汞电极相比，所有化合物在CO2的第一次还原电势下均表现出电催化电流增强，其范围为-1.53 V至-1.96V。在四小时的制备规模电解中，所有物种均观察到催化性CO生成，但是在X不是Br的化合物中检测到大量的H-2。所有物种最终都会在350 nm和420 nm的光下分解，但是由于蓝移MLCT带，在420 nm的光下氰化物取代的络合物（X = CN）的寿命更长（最多5倍）。

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《Dalton transactions: An international journal of inorganic chemistry》 |2015年第5期|共10页
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Agarwal Jay; Stanton Charles J. III; Shaw Travis W.; Vandezande Jonathon E.; Majetich George F.; Bocarsly Andrew B.; Schaefer Henry F. III;
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1. Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)(3)] complexes [J] . Agarwal Jay, Stanton Charles J. III, Shaw Travis W., Dalton transactions: An international journal of inorganic chemistry . 2015,第5期

机译：探索轴向配体取代（X = Br，NCS，CN）对[MnX（N-C）（CO）（3）]配合物的光分解和电化学活性的影响
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Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)(3)] complexes

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