A stable phosphanyl phosphaketene and its reactivity.
Sodium phosphaethynolate, Na(OCP), reacts with the bulky P-chloro-diazaphosphole yielding a phosphanyl phosphaketene, which is stable for weeks under an inert atmosphere in the solid state. This compound is best described as a tight ion pair with a remarkably long P-P bond distance (2.44 Å). In solution, this phosphaketene dimerizes under loss of CO to give 1,2,3-triphosphabicyclobutane identified by an X-ray diffraction study. As an intermediate, a five-membered heterocyclic diphosphene was trapped in a Diels-Alder reaction with 2,3-dimethylbutadiene. The formation of this intermediate in a hetero-Cope-rearrangement as well as dimerization/CO loss were computed with various DFT methods which allowed us to understand the reaction mechanisms.
Lehn Institute of Functional Materials (LIFM), Sun Yat-Sen University, 510275 Guangzhou, China. hgruetzmacher@ethz.ch.
Zhongshu
Z
Li
Xiaodan
X
Chen
Maike
M
Bergeler
Markus
M
Reiher
Cheng-Yong
CY
Su
Hansjörg
H
Grützmacher