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Reaction of Hexachlorocyclotriphosphazene with Sodium p‐Cresoxide
Author(s) -
Karthikeyan S.,
Krishnamurthy S. S.
Publication year - 1984
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19845130627
Subject(s) - geminal , chemistry , sodium , yield (engineering) , medicinal chemistry , substitution reaction , phosphorus , nuclear magnetic resonance spectroscopy , tris , oxygen , stereochemistry , organic chemistry , biochemistry , materials science , metallurgy
The reaction of hexachlorocyclotriphosphazene (N 3 P 3 Cl 6 ) with sodium p‐cresoxide proceeds by a predominantly nongeminal pathway. The presence of geminal isomers at the bis‐ and tris‐stages of substitution in tiny quantities (< 5%) has also been observed. All the chloro(p‐cresoxy)cyclotriphosphazenes and their dimethylamino derivatives have been characterized by 1 H‐, 13 C{ 1 H}‐, and 31 P{ 1 H}‐NMR spectroscopy. The reaction of N 3 P 3 Cl 6 with sodium phenoxide has been reinvestigated. The relative yields of the products at various stages of substitution and their isomeric compositions are almost the same for both phenoxy and p‐cresoxy systems. Possible mechanisms to explain the observed isomeric compositions are discussed. A “through‐space” interaction involving oxygen‐2p and phosphorus‐3d orbitals is invoked to explain the greater yield of the cis isomer of N 3 P 3 Cl 4 (OAr) 2 than that of its trans isomer.