Issue 8, 1984

Geminal bis[(triphenylphosphoranylidene)amino]cyclotriphosphazenes synthesis: substitution reactions, and nuclear magnetic resonance spectra

Abstract

Cyclotriphosphazenes bearing an amino ligand are readily converted into the corresponding (triphenylphosphoranylidene)amino (–N[double bond, length half m-dash]PPh3) derivatives by means of an excess of triphenylphosphine–tetrachloromethane in an acetonitrile–triethylamine medium (Appel reaction). Thus prepared, N3P3Cl4(N[double bond, length half m-dash]PPh3)2 reacts with dimethylamine in various solvents according to a geminal substitution pattern; this is an indication of SN1-type reactions, as a result of the strong electron-donating character of the ligands. The ultimate substitution product N3P3(NMe2)4(N[double bond, length half m-dash]PPh3)2, also prepared from N3P3(NMe2)4(NH2)2, is isolated as its HCl or 2HCl adduct, depending on the method of preparation. In both adducts the protons are attached to ring nitrogen atoms, and variable-temperature 1H and 31P n.m.r. measurements show prototropic behaviour at elevated temperatures. Trends within the 31P n.m.r. parameters of the derivatives are discussed in terms of the electron-donating ability of the ligands.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1984, 1521-1526

Geminal bis[(triphenylphosphoranylidene)amino]cyclotriphosphazenes synthesis: substitution reactions, and nuclear magnetic resonance spectra

C. Lensink, B. de Ruiter and J. C. van de Grampel, J. Chem. Soc., Dalton Trans., 1984, 1521 DOI: 10.1039/DT9840001521

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