Hoidn Christian M, Maier Thomas M, Trabitsch Karolina, Weigand Jan J, Wolf Robert
University of Regensburg, Institute of Inorganic Chemistry, 93040, Regensburg, Germany.
TU Dresden, Faculty of Chemistry and Food Chemistry, 01062, Dresden, Germany.
Angew Chem Int Ed Engl. 2019 Dec 19;58(52):18931-18936. doi: 10.1002/anie.201908744. Epub 2019 Nov 7.
The activation of white phosphorus (P ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion 5 and 1-cyanodiphosphan-1-ide anions [R PPCN] (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P fragment.
过渡金属配合物对白磷（P）的活化已研究了数十年，但所得（有机）磷配体的官能化和释放却鲜有实现。在此，我们描述了通过用氰化物处理，由一个P配体形成罕见的二膦-1-亚胺阴离子。二有机五磷钴配合物是通过一个逐步反应序列合成的，该序列涉及低价二亚胺钴配合物、白磷和二有机氯膦。这些配合物与四烷基铵或氰化钾的反应产生了一个环三磷钴酸根阴离子5和1-氰基二膦-1-亚胺阴离子[R PPCN]（6-R）。一个相关产物7的分子结构表明了一种新颖的反应机制，其中氰根阴离子与钴中心的配位引发了配体重排。随后，第二个氰根阴离子对一个磷原子进行亲核进攻并释放出P片段。
