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A Tetracyclic Octaphosphane by Successive Addition, Inversion, and Condensation Reactions
Author(s) -
Hennersdorf Felix,
Weigand Jan J.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201703953
Subject(s) - chemistry , amide , stereochemistry , condensation reaction , crystal structure , crystallography , organic chemistry , catalysis
An example of an octaphosphane of type R 2 P 8 (R=(DDP)Ga) was isolated by treatment of cage compound (DDP)GaP 4 ( 2 , DDP=(2,6‐diisopropylphenyl)(4‐((2,6‐diisopropylphenyl)imino)pent‐2‐en‐2‐yl)amide) with (C 6 F 5 ) 2 PBr. The initially formed endo ‐ exo butterfly shaped pentaphosphane 7 rapidly rearranges to the more stable exo – exo isomer 8 , which undergoes dimerization to decaphosphane 11 . Compound 11 unexpectedly eliminates tetraaryldiphosphane 13 to give tetracyclo[3.3.0.0 2,7 .0 4,6 ]octaphosphane [(DDP)GaBr] 2 P 8 ( 12 ). The reaction steps were confirmed by crystal structure analysis of the key intermediates and supported by kinetic studies using NMR techniques.