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An unusual way of formation of spirophosphoranes during the oxidative addition of hexafluoroacctone to σ 5 P‐σ 3 P‐diphosphorus compounds, and in the reaction of 2‐chloro‐l,2‐dimethyl‐3‐phenyl‐2‐phenylseleno‐l,3,5σ 5 ‐diazaphosphetidin‐4‐one with bis(2‐chloroethyl)amine hydrochloride/ triethylamine
Author(s) -
Neda Ion,
Pinchuk Vasily A.,
Thönnessen Holger,
Ernst Ludger,
Jones Peter G.,
Schmutzler Reinhurd
Publication year - 1997
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19976230825
Subject(s) - chemistry , oxidative phosphorylation , oxidative addition , medicinal chemistry , radiochemistry , organic chemistry , catalysis , biochemistry
The reaction of (chloromethyl)dichlorophosphine 1 with N,N′‐dimethyl‐N,N′‐bis(trimethylsilyl)urea 2 furnished the σ 5 P‐σ 3 P‐diphosphorus compound 3 . The reaction of 3 with hexafluoroacetone proceeded in an unusual fashion, with the rupture of the PP bond, resulting in 4,4‐bis(trifluoromethyl)‐3‐chloro‐2‐hexfluoroisopropoxy‐2‐oxo‐1,2‐oxaphosphetane 7 and the spirophosphorane 4‐chloromethyl‐1,3,5,7‐tetramethyl‐1,3,5,7‐tetraaza‐4σ 5 ‐phosphaspiro‐[3,3]heptan‐2,6‐dione 8 . The reaction of 2‐chloro‐1,2‐dimethyl‐3‐phenyl‐2‐phenylseleno‐1,3,2σ 5 ‐diazaphosphetidin‐4‐one 9 with bis(2‐chloroethyl)amine hydrochloride/triethylamine 10 also proceeded in an unexpected fashion, leading to the spirophosphorane 11 as the only identified product. Single‐crystal X‐ray structure analyses of compounds 8 and 11 were conducted. The coordination geometry at phosphorus in both compounds shows a large deviation from idealized forms. This distortion arises mainly from the presence of the four‐membered rings.