Hanson Samuel S, Doni Eswararao, Traboulsee Kyle T, Coulthard Graeme, Murphy John A, Dyker C Adam
Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3 (Canada).
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL (UK).
Angew Chem Int Ed Engl. 2015 Sep 14;54(38):11236-9. doi: 10.1002/anie.201505378. Epub 2015 Jul 24.
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 SN bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.
一种新的基态有机电子供体已被制备出来，它在双吡啶叉骨架上具有四个强π供电子的亚氨基膦取代基。循环伏安法显示，对于涉及中性有机供体及其二价阳离子的电对，相对于饱和甘汞电极（SCE），其氧化还原电位达到了创纪录的-1.70 V。这种高还原性有机化合物可以被分离出来（产率44 %），或者更方便地通过涉及其易于制备的吡啶鎓离子前体的去质子化反应原位生成。该供体能够还原多种芳基卤化物，并且由于其氧化还原电位，它被发现是第一种在热诱导的N,N-二烷基磺酰胺的SN键还原裂解以及丙二腈的还原加氢脱氰反应中有效的有机供体。
