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Abstract
A series of new nongeminally-substituted cyclic phosphazenes with various substituents has been prepared via deprotonation-substitution reactions at the Me groups of both the cis and trans isomers of [(Me)(Ph)PN] 3 . Treatment of [(Me)(Ph)PN] 3 with n-BuLi followed by reaction with organic electrophilic reagents affords a variety of cyclic derivatives, [(RCH 2 )(Ph)PN] 3 , [R = Me, Cl, Br, I, (CH 2 ) 2 Br, CH 2 CH═CH 2 , SR, C(═O)OLi, C(═O)OMe, C(═O)OEt]. The structures of theses cis cyclic phosphazenes, which were obtained by x-ray diffraction, illustrate the basket-like shape of the molecules. Heating the cis and trans isomers of the parent [(Me)(Ph)PN] 3 produced mixtures of cyclic trimers and tetramers. The latter were isolated and characterized by x-ray crystallography. Nanoparticles of gold and silver were prepared by reduction of metal salts with a reducing agent in the presence of selected trimers.
The authors thank the Robert A. Welch Foundation, the Petroleum Research Fund administered by the American Chemical Society, and the National Science Foundation for generous financial support.