New molecular topologies from main group elements P N B N and Al N containing macrocycles and pyridinophanes

Abstract

This newlinechapter newlinedemonstrates newlinethe newlinestepwise newlinefunctionalization newlineof newlinethe newlinechlorophosph(III)azane, [ClP(and#956;-NtBu)] 2 with organic azides and chalcogens (S and Se). newlineThe progress of these reactions were followed by in-situ newline31 newlineP{ 1 H} NMR revealing that newlineconversion of basic (P III ) 2 N 2 framework leading to (P V ) 2 N 2 proceed via mixed valent newline(P III /P V )N 2 intermediates. These (P III /P V )N 2 intermediate species provide details of the newlinereaction pathway and distribution of cis and trans isomers of (P V ) 2 N 2 products and can be newlineisolated under controlled conditions. The work also demonstrates the expedient formation newlineof (P V ) 2 N 2 products at elevated temperature under neat condition without significantly newlineaffecting the yields and relative distribution of cis and trans isomers. All new compounds newlinereported here are potential building blocks for the assembly of inorganic macrocycles and newlinepolymers and have been characterized thoroughly using different techniques including newlinesingle crystal X-ray diffraction, multinuclear NMR, IR and high resolution mass newlinespectrometry. newline