Phosphacycloalkyldiones: synthesis and coordinative behaviour of 6- and 7-member cyclic diketophosphanyls
作者:Kyle G. Pearce、Vladimir Simenok、Ian R. Crossley
DOI:10.1039/d0dt00864h
日期:——
Glutaryl and adipoyl chlorides undergo facile condensation with the bis(silyl)phosphanes RP(SiMe3)2 (R = Me, nBu, tBu, Ph, Mes) to afford exclusively the phosphacycloalkyldiones (CH2)n(C[double bond, length as m-dash]O)2PR (n = 3, 4). Characterised spectroscopically and, for R = Ph, Mes (n = 3) crystallographically, the macrocycles are conformationally fluxional in solution and appreciably moisture
戊二酰氯和己二酰氯与双(甲硅烷基)膦RP(SiMe3)2(R = Me,nBu,tBu,Ph,Mes)容易缩合,仅得到磷环烷基二酮(CH2)n(C [双键,长度为m -破] O)2 PR(n = 3、4)。在光谱上表征,对于R = Ph,在结晶学上为Mes(n = 3)表征,大环在溶液中呈构象流动,并且对水分敏感。尽管看似对磷的化学氧化具有抗性,但很容易实现配位,如反式-[Pt(PEt3)P(Ph)(CO)2(CH2)3} Cl2]和一系列五羰基钨配合物的分离所示,通过结晶学,红外光谱和NMR光谱对其进行表征。这些数据共同表明,大环是相对弱的σ供体,没有明显的π受体特征。