作者:Keith B. Dillon、Martin P. Nisbet、Thomas C. Waddington
DOI:10.1039/dt9790000883
日期:——
The reactions of PX3(X = Cl, Br, or I) with the strongly acidic solvents 100% H2SO4, 25 and 65 oleum, HSClO3 and HSFO3, have been investigated by means of 31P n.m.r. spectroscopy. The usual initial reaction is oxidation to [PX3(OH)]+, although HSClO3 also forms [PX3Cl]+. The reduction in acid strength which necessarily accompanies the redox reaction promotes solvolysis of P–X bonds, and halogen exchange
PX的反应3(X =氯,溴,或I)用强酸性溶剂100%H 2 SO 4,25和65的发烟硫酸,HSClO 3和HSFO 3,已经通过的方法,研究31 P NMR光谱。通常的初始反应是氧化为[PX 3(OH)] +,尽管HSClO 3也形成[PX 3 Cl] +。氧化还原反应必不可少的酸强度的下降会促进P-X键的溶剂分解,并促进HSClO 3和HSFO 3中的卤素交换。由PBr形成[PBr 4 ] +在几种溶剂中也观察到3。在溶液中发现了一些有趣的新物种,尤其是含有P–I键的磷( V)阳离子,但在25个发烟硫酸中却未发现。在65发烟硫酸中可能发生涉及消除HBr或HI的缩合反应。提出了观察到的各种反应的可能机理。