Pushing the limits of neutral organic electron donors: a tetra(iminophosphorano)-substituted bispyridinylidene.
Pushing the limits of neutral organic electron donors: a tetra(iminophosphorano)-substituted bispyridinylidene.
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DOI：
10.1002/anie.201505378
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发表时间：
2015-09-14
期刊：
影响因子：
--
通讯作者：
Dyker CA
中科院分区：
文献类型：
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作者：
Hanson SS;Doni E;Traboulsee KT;Coulthard G;Murphy JA;Dyker CA
制备了一种新的基态有机电子给体，其特征是在双吡啶骨架上有四个强烈给π的亚胺基膦取代基。循环伏安法显示，对于中性有机供体及其阳离子，其氧化还原电位为−1.70 V与饱和甘汞电极(SCE)的氧化还原电位之比为1.70。这种高度还原的有机化合物可以分离出来(44 %)，或者更方便地在 原位通过与其容易制备的吡啶离子前驱体的去质子化反应生成。该给电子体能够还原多种芳基卤化物，并且由于其氧化还原电势，被发现是第一个在热诱导N，N-二烷基磺酰胺的还原S-N键断裂和丙二腈的还原氢脱氰化反应中有效的有机给电子体。
A new ground-state organic electron donor has been prepared that features four strongly π-donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of −1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S–N bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.