Synthesis and Rearrangement of P-Nitroxyl-Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study
Synthesis and Rearrangement of P-Nitroxyl-Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study
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对硝酰基取代的 PIII 和 PV 膦的合成和重排：实验与理论相结合的案例研究
DOI：
10.1002/chem.201504900
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Rainer Streubel
中科院分区：
文献类型：
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作者：
Tobias Heurich;Zheng-Wang. Qu;Senada Nozinnovic;Gregor Schnakenburg;Hideto Matsuoka;Stefan Grimme;Olav Schiemann;Rainer Streubel
低温生成P-硝酰基膦2（Ph 2 POTEMP），其通过Ph 2 PH（1）与两当量克里思反应获得。在升温时，膦2分解为最终产物之一P-硝酰基膦P-氧化物3（Ph 2 P（O）OTEMP）。这种简单的合成方法还可以通过使用Ph 2 P（S）H（6）或Ph 2 P（BH 3）H（11）和克里思分别获得P-硫化物和P-硼烷衍生物7和13。硫化膦7在室温下在CDCl 3中重排为氧化膦8（Ph 2 P（O）STEMP），而在THF中，硫化物7的热分解产生盐10（[TEMP-H2][Ph 2 P（S）O]）。除了EPR和详细的NMR动力学研究之外，深入的理论研究还提供了对反应途径和反应中间体自旋密度分布的深入了解。
Low‐temperature generation ofP‐nitroxyl phosphane2(Ph2POTEMP), which was obtained by the reaction of Ph2PH (1) with two equivalents of TEMPO, is presented. Upon warming, phosphane2decomposed to giveP‐nitroxyl phosphaneP‐oxide3(Ph2P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access toP‐sulfide andP‐borane derivatives7and13, respectively, by using Ph2P(S)H (6) or Ph2P(BH3)H (11) and TEMPO. Phosphane sulfide7revealed a rearrangement to phosphane oxide8(Ph2P(O)STEMP) in CDCl3at ambient temperature, whereas in THF, thermal decomposition of sulfide7yielded salt10([TEMP‐H2][Ph2P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates.