Synthesis of Heavy Dicyanamide Homologues from Air-Stable Precursors
Synthesis of Heavy Dicyanamide Homologues from Air-Stable Precursors
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DOI：
10.1002/chem.201803941
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发表时间：
2018-10-01
影响因子：
4.3
通讯作者：
Macdonald, Charles L. B.
中科院分区：
文献类型：
--
作者：
Binder, Justin F.;Kosnik, Stephanie C.;Macdonald, Charles L. B.
报道了一种简便的合成二氰磷和二氰砷阴离子的方法。这些重同系物的长期已知的和根本上重要的双氰胺阴离子的形成通过亲核取代双（二苯基膦基）乙烷（dppe）从磷属元素（+）转移剂[dppePn][BPh 4]（Pn = P，As）通过暴露于氰化物盐。该方案需要三个合成步骤，从商业上可获得的材料和[dppePn][BPh 4]盐是显着的温度，空气和水分稳定。所有的产品已被充分的光谱方法和单晶X-射线衍射，其特征在于，和DCPn阴离子的电子结构进行了评估计算。
A convenient synthesis of dicyanophosphide and dicyanoarsenide anions is reported. These heavy homologues of the long-known and fundamentally important dicyanamide anion were formed through the nucleophilic displacement of bis(diphenylphosphino)ethane (dppe) from the pnictogen(+) transfer agents [dppePn][BPh4] (Pn = P, As) by exposure to cyanide salts. The protocol requires three synthetic steps from commercially available materials and the [dppePn][BPh4] salts are remarkably temperature, air, and moisture stable. All products have been fully characterized by spectroscopic methods and by single-crystal X-ray diffraction, and the electronic structures of the DCPn anions have been assessed computationally.