Phosphorus-nitrogen compounds (Part 51): the relationship between spectroscopic and crystallographic data of mono- and di- spiro cyclophosphazene derivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms.

Aytuğ Okumuş,Nuran Asmafi̇li̇z,Gamze Elmas,Zeynel Kiliç,Selen Bi̇lge Koçak

doi:10.3906/kim-1911-43

Abstract

A great wealth of structural information about phosphazenes can be gleaned from the combined spectroscopic and crystallographic data. When data from 31P NMR spectroscopy and X-ray crystallography are put together like pieces in a puzzle, a number of correlations can be obtained for phosphazene derivatives. A systematic study concerning the correlations among the structural parameters (e.g., 31P NMR data, endocyclic/exocyclic NPN bond angles and bond lengths) revealed some characteristics of mono- and di- spiro cyclophosphazene derivatives bearing 4-fluoro/nitrophenylmethyl pendant arm/arms. These correlations include the relationship between the δ Pspiro shifts, the values of electron density transfer parameters Δ(P–N), and the endocyclic and exocyclic NPN bond angles of the cyclophosphazenes. The structural parameters were compared with each other for 19 compounds of 5 different architectural types of cyclophosphazenes with 5- to 7-membered spiro -rings.

Highlights

Since 1960, the Cl-replacement reactions of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene with monodentate [1,2] and bidentate [3] reagents have been extensively studied
A large number of papers published by our research group are available on cyclophosphazenes that provide information on their structures, synthesis, and biological activities; the present study focuses on correlation among the structural parameters of mono- and di-spirocyclophosphazene derivatives with 4fluoro/nitrophenylmethyl pendant arm/arms
As a particular interest in our ongoing studies on phosphazene-based chemistry, the present study primarily focuses on a number of correlations established among the structural parameters in mono- and di-spirocyclophosphazene derivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms of the compounds previously synthesized and published by our research group (Table 1) [49,50,51,52,57,58,59]

Summary

Introduction

Since 1960, the Cl-replacement reactions of hexachlorocyclotriphosphazene (trimer, N 3 P 3 Cl 6) and octachlorocyclotetraphosphazene (tetramer, N 4 P 4 Cl 8) with monodentate [1,2] and bidentate [3] reagents have been extensively studied. Here we report our findings on the relationship among the δ P spiro shifts with endocyclic and exocyclic NPN bond angles, and electron density transfer parameters, and a brief description of the synthesis methods of 5 types and a total of 19 cyclotri/tetraphosphazenes containing 4-fluoro/nitrophenylmethyl pendant arm and 5- to 7-membered spiro-rings.

Results

Conclusion