Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions
作者:Yu. S. Panova、A. V. Khristolyubova、V. V. Sushev、N. V. Zolotareva、M. D. Grishin、E. V. Baranov、G. K. Fukin、A. N. Kornev
DOI:10.1007/s11172-021-3305-1
日期:2021.10
ketone, propiophenone, and indan-2-one were studied in the reaction with phosphorus(ɪɪɪ) chloride. The possibility of the formation of 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes is largely determined by the nature of the starting ketazine. Diazadiphosphapentalene dichlorides exist in solution as a mixture of cis- and trans-isomers, but crystallize exclusively as 1,4-trans-isomers. Reduction of 3a
在反应中研究了诸如苯乙酮及其取代衍生物(p- F、m- Cl、p- I、p- Me、p- OMe)、丙酮、二苄基酮、苯丙酮和茚满-2-酮的吖嗪类酮嗪与磷(ɪɪɪ)氯化物。形成 1,4-二氯-3a,6a-二氮杂-1,4-二磷杂戊烯的可能性在很大程度上取决于起始酮嗪的性质。二氮杂二磷戊烯二氯化物以顺式和反式异构体的混合物存在于溶液中,但仅以 1,4-反式结晶-异构体。在四氢呋喃中用锰还原 3a,6a-diaza-1,4-diphosphapentalene 二氯化物得到相应的 diazadiphosphapentalene,产率为 52-63%。通过循环伏安法研究所得化合物的电化学性质。发现 3a,6a-二氮杂-1,4-二磷戊烯的两种二氯化物具有 0.29 和 0.13 V 的异常氧化电位,这与在供体溶剂的影响下歧化形成溶液中游离二氮杂二磷戊烯有关,这是通过31 P NMR 光谱、电子吸收光谱和独立合成证实。