Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P2 N-Ring Ligand.
Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P2 N-Ring Ligand.
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DOI：
10.1002/chem.201600850
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发表时间：
2016-10
期刊：
影响因子：
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通讯作者：
P. K. Majhi;A. W. Kyri;Alexander Schmer;G. Schnakenburg;R. Streubel
中科院分区：
文献类型：
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作者：
P. K. Majhi;A. W. Kyri;Alexander Schmer;G. Schnakenburg;R. Streubel
通过Li/Cl膦酰亚胺配合物2与各种伯胺（R=Me、iPr、tBu、Cy、Ph）的反应实现了1，1 '-双官能氨基膦配合物3a-e的合成。络合物3a（R=Me）与六甲基二硅氮钾的去质子化产生K/NHMe膦酰亚胺络合物4a和膦酰氨基钾络合物4a '的混合物。用KHMDS处理络合物3c（R=tBu）和e（R=Ph）得到K/NHR膦酰类络合物4c和e的第一个实例。配合物3c与2摩尔当量的KHMDS反应，然后与PhPCl 2反应，得到具有P2 N-环配体的配合物5c、c '。通过NMR、IR、MS和微量分析对所有配合物进行了表征，另外，通过单晶X射线晶体学对配合物3b-e和5 c'进行了仔细检查。
Synthesis of 1,1'-bifunctional aminophosphane complexes 3 a-e was achieved by the reaction of Li/Cl phosphinidenoid complex 2 with various primary amines (R=Me, iPr, tBu, Cy, Ph). Deprotonation of complex 3 a (R=Me) with potassium hexamethyldisilazide yielded a mixture of K/NHMe phosphinidenoid complex 4 a and potassium phosphanylamido complex 4 a'. Treatment of complex 3 c (R=tBu) and e (R=Ph) with KHMDS afforded the first examples of K/NHR phosphinidenoid complexes 4 c and e. The reaction of complex 3 c with 2 molar equivalents of KHMDS followed by PhPCl2 afforded complexes 5 c,c', which possess a P2 N-ring ligand. All complexes were characterized by NMR, IR, MS, and microanalysis, and additionally, complexes 3 b-e and 5 c' were scrutinized by single-crystal X-ray crystallography.