Product Isomer Distribution in the Sequential Functionalization of Cyclic PIII 2N2 Frameworks

Abstract

We have demonstrated stepwise functionalization ofchlorophosph(III)azane, [ClP(μ-NtBu)]2with organic azides andchalcogens (S and Se). The in situ31P{1H} NMR spectroscopicinvestigations reveal that conversion of the basic PIII2N2frame-work, leading to PV2N2proceeds via (PIII/PV)N2intermediates.Under controlled conditions, the (PIII/PV)N2intermediate speciescan be isolated, providing details of the reaction pathway and distribution of thecisandtransisomers of the PV2N2products.It has also been demonstrated that neat reactions at elevatedtemperatures expedite the formation of PV2N2products, with-out significantly affecting the yields and relative distribution ofthecisandtransisomers. All new compounds reported hereare potential building blocks for the assembly of inorganicmacrocycles and polymers.