Cycloalkylaminocyclo- and Polyphosphazenes:  X-ray Crystal Structures ofgem-Tetrakis(cyclohexylamino)dichlorocyclotriphosphazene and Octakis(cyclopropylamino)cyclotetraphosphazene

Abstract

The reactions of chlorocyclophosphazenes N3P3Cl6 (1) and N4P4Cl8 (2) and polydichlorophosphazene (3) with cyclohexylamine, cyclopentylamine, and cyclopropylamine have been studied. The major product with 1 is the geminal tetrakis derivative N3P3Cl2(NHR)4, while 2 gives the completely substituted derivative, N4P4(NHR)8. X-ray crystal structure determinations of N3P3Cl2(NHC6H11)4 (1a) and N4P4(NHC3H5)8 (2c) have been carried out. 1a crystallizes in a triclinic space group, P1, with a = 11.2330(13) Å, b = 11.4269(16) Å, c = 13.4055(12) Å, α = 72.211(10)°, β = 72.150(9)°, γ = 81.777(11)°, V = 1557.3(3) Å3, and Z = 2. 2c crystallizes in a monclinic space group, P21/n, with a = 12.433(3) Å, b = 20.484(4) Å, c = 12.645(3) Å, β = 92.81(2)°, V = 1557.3(3) Å3, and Z = 4. The cycloalkylamino-substituted polyphosphazenes contain a small amount of residual chlorine atoms. These have high glass transition temperatures.

Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo‐triplet splitting

“…The optimized structure is shown in Fig. 2 2 , obtained from the ab initio calculations at HF/6-311G** and B3LYP/6-311G** levels (H atoms are omitted for clarity). SCHEME 2 The atom-labeling scheme for the optimized structure of compound 6 (H atoms are omitted for clarity).…”

“…The chemistry of small inorganic heterocycles of the type (P N) 2 researches [1][2][3], mainly because such molecules are good starting materials for polycyclic inorganic and organometallic compounds [4,5]. The wide range applications of cyclophosphazanes in nucleophilic substitution reactions on P Cl bonds [6,7], coordination chemistry [8], and ring-opening polymerization reactions [9] causes a significant attraction to this area of chemistry.…”

High Molecular Weight Phosphazene Copolymers Having Chemical Functions Inside Chiral Pockets Formed by (R)‐(1,1′‐Binaphthyl‐2,2′‐dioxy)phosphazene Units

“…In fact, the Tg of 1 (296°C) is the highest glass transition recorded for a phosphazene high molecular weight polymer [up to now the highest reported Tg is 220°C for a poly(aminophosphazene)]. [16] This, together with the broad NMR spectra at room temperature and the observed sharpness upon heating evidenced the high stereochemical rigidity of the polymeric chains, which, in principle, is helpful in their potential use as ligands to support catalysts for asymmetric reactions.…”

Synthesis and Characterization of a New Cyclophosphazene and Its Ruthenium Complex Derived from 1,10-Phenanthroline-5,6-diol

“…The usage of cyclophosphazenes as ligands for transition metals is another area of interest. Coordination through a ring nitrogen atom and/or an appropriately substituted ligand group can lead to a number of interesting structures 12 .…”