Abstract
The geometry of the five-membered ring ( 1) containing a phosphinyl radical is studied by ab initio molecular orbital calculations. X-irradiation of a single crystal of 1,3-benzazaphosphole ( 2) generates the cyclic phosphinyl radical ( 3) whose EPR parameters are obtained and compared with those calculated for 1. Experimental and calculated results show that, in 3, the five-membered ring adopts a distorted “envelope” structure and that a rapid inversion motion occurs at room temperature.
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