[Cr(pincer(2-))](2) as an electron shuttle for reductively promoted hydrazine disproportionation

Labrum Nicholas S.; Caulton Kenneth G.

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[Cr(pincer(2-))](2) as an electron shuttle for reductively promoted hydrazine disproportionation

机译：[Cr（钳子（2 - ））]（2）作为未经化的促进肼的电子往返

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We describe here delivery of hydrazine to a reducing, low oxidation state chromium bound to a proton responsive ligand which has already been deprotonated. Reaction of PhHNNH2 at a 4 : 1 mole ratio with the bis-(pyrazolate)pyridyl pincer ligated reducing agent [(CrL)-L-II](2) gives prompt conversion to [CrIII2L(2)(PhNH2)(2)(mu-PhHNN)], with release of NH3 and C6H6, a new disproportionation of the hydrazine, with trapping of PhHNN as its dianion, bridging the two chromium centers. The redox balance of the reaction is discussed, and participation by Bronsted basic sites on the bis-(pyrazolate)pyridyl pincer ligand L2- is suggested, but no hydrazine protons remain on the pincer in the product.

机译：在此描述肼向还原的低氧化态铬递送，该铬结合已被脱质的质子响应配体。 PHHNNH2在4：1摩尔比与双 - （吡唑酸盐）吡啶基钳子连接还原剂[（CRL）-L-II]（2）的反应给予[CRII2L（2）（PHNH2）（2）（ MU-PHHNN）]，释放NH3和C6H6，肼的新歧化，具有捕获PHHNN作为其脱振，桥接两个铬中心。讨论了反应的氧化还原平衡，并提出了BIS-（吡唑酸酯）吡啶基钳子配体L2-的铜稳基碱性位点，但在产品中没有肼质子留在夹持子上。

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《Dalton transactions: An international journal of inorganic chemistry》 |2019年第31期|共5页
作者
Labrum Nicholas S.; Caulton Kenneth G.;
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Indiana Univ Dept Chem Bloomington IN 47405 USA;

Indiana Univ Dept Chem Bloomington IN 47405 USA;

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正文语种 eng
中图分类化学;无机化学;
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1. [Cr(pincer(2-))](2) as an electron shuttle for reductively promoted hydrazine disproportionation [J] . Labrum Nicholas S., Caulton Kenneth G. Dalton transactions: An international journal of inorganic chemistry . 2019,第31期

机译：[Cr（钳子（2 - ））]（2）作为未经化的促进肼的电子往返
2. Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials [J] . Wang Qiang, Huang Liping, Pan Yuzhen, Journal of Hazardous Materials . 2017,第jana5期

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3. High-pH and anoxic conditions during soil organic matter extraction increases its electron-exchange capacity and ability to stimulate microbial Fe(III) reduction by electron shuttling [J] . Yuge Bai, Edisson Subdiaga, Stefan B. Haderlein, Biogeosciences . 2020,第3期

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4. BIOLOGICAL AND ABIOTIC REACTIONS WITH IRON AND ELECTRON SHUTTLES THAT PROMOTE HEXAHYDRO-1,3,5-TRINITRO-1,3,5-TRIAZINE (RDX) DEGRADATION [C] . Kevin T. Finneran American Chemical Society Division of Environmental Chemistry Symposium . 2008

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5. Redox-Active Pincer Ligands on Chromium: An Electron Shuttle for Reductive Transformations of Carbon Dioxide, Diazene, and Hydrazine [D] . Labrum, Nicholas Scott 2019

机译：铬上的具有氧化还原活性的钳子配体：一种用于二氧化碳，二氮杂苯和肼的还原转化的电子梭
6. Extracellular Electron Transport-Mediated Fe(III) Reduction by a Community of Alkaliphilic Bacteria That Use Flavins as Electron Shuttles [O] . Samuel J. Fuller, Duncan G. G. McMillan, Marc B. Renz, 2014

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8. Photochemical Disproportionation Reactions of the W2(CO)10(2-) and Fe2(CO)8(2-) Complexes [R] . Silavwe, N. D., Pan, X., Tyler, D. R. 1988

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[Cr(pincer(2-))](2) as an electron shuttle for reductively promoted hydrazine disproportionation

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