The Partial Aminolysis of (NPF2)3, 4

T. L. Evans; H. R. Allcock

doi:10.1021/ic50199a002

The Partial Aminolysis of (NPF₂)_{3, 4}

T. L. Evans, H. R. Allcock

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Abstract

Unlike the reactions of (NPCI₂H₄ with simple amines, the fluorocyclophosphazenes,(NPF₂)3^f₄, react withmethylamine, n-butylamine, or dimethylamine with replacement of only one fluorine atom per phosphorus to yield products such as N₄P₄F⁵(NHMe)₃, N₄P₄F₄(NHMe)₄, N₄P₄F⁵(NHC₄H₉)₃, N₄P₄F⁵(NMe₂)₃, N₄P₄F₄(NMe₂)₄, N₃P₃F₄(NHMe)₂, N₃PrF₄(NHC₄HS)₂, or N₃P₃F₄(NMe₂)₂. This behavior cannot be ascribed to steric effects because nuclcophiles such as CF₃CH₂ONa, C₆H₅ONa, and (CH₃)₂NLi readily replace all the fluorine atoms. The results are more compatible with an explanation based on the poor leaving-group ability of fluoride combined with the low nucleophilicity of the free amines, compared with the higherleaving-group ability of chloride and the high nucleophilicity of alkoxides, aryl oxides, or metal amides.

Original language	English (US)
Pages (from-to)	2342-2344
Number of pages	3
Journal	Inorganic chemistry
Volume	18
Issue number	9
DOIs	https://doi.org/10.1021/ic50199a002
State	Published - Feb 1 1979

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "The Partial Aminolysis of (NPF2)3, 4",

abstract = "Unlike the reactions of (NPCI2H4 with simple amines, the fluorocyclophosphazenes,(NPF2)3f4, react withmethylamine, n-butylamine, or dimethylamine with replacement of only one fluorine atom per phosphorus to yield products such as N4P4F5(NHMe)3, N4P4F4(NHMe)4, N4P4F5(NHC4H9)3, N4P4F5(NMe2)3, N4P4F4(NMe2)4, N3P3F4(NHMe)2, N3PrF4(NHC4HS)2, or N3P3F4(NMe2)2. This behavior cannot be ascribed to steric effects because nuclcophiles such as CF3CH2ONa, C6H5ONa, and (CH3)2NLi readily replace all the fluorine atoms. The results are more compatible with an explanation based on the poor leaving-group ability of fluoride combined with the low nucleophilicity of the free amines, compared with the higherleaving-group ability of chloride and the high nucleophilicity of alkoxides, aryl oxides, or metal amides.",

author = "Evans, {T. L.} and Allcock, {H. R.}",

year = "1979",

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T1 - The Partial Aminolysis of (NPF2)3, 4

AU - Evans, T. L.

AU - Allcock, H. R.

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Y1 - 1979/2/1

N2 - Unlike the reactions of (NPCI2H4 with simple amines, the fluorocyclophosphazenes,(NPF2)3f4, react withmethylamine, n-butylamine, or dimethylamine with replacement of only one fluorine atom per phosphorus to yield products such as N4P4F5(NHMe)3, N4P4F4(NHMe)4, N4P4F5(NHC4H9)3, N4P4F5(NMe2)3, N4P4F4(NMe2)4, N3P3F4(NHMe)2, N3PrF4(NHC4HS)2, or N3P3F4(NMe2)2. This behavior cannot be ascribed to steric effects because nuclcophiles such as CF3CH2ONa, C6H5ONa, and (CH3)2NLi readily replace all the fluorine atoms. The results are more compatible with an explanation based on the poor leaving-group ability of fluoride combined with the low nucleophilicity of the free amines, compared with the higherleaving-group ability of chloride and the high nucleophilicity of alkoxides, aryl oxides, or metal amides.

AB - Unlike the reactions of (NPCI2H4 with simple amines, the fluorocyclophosphazenes,(NPF2)3f4, react withmethylamine, n-butylamine, or dimethylamine with replacement of only one fluorine atom per phosphorus to yield products such as N4P4F5(NHMe)3, N4P4F4(NHMe)4, N4P4F5(NHC4H9)3, N4P4F5(NMe2)3, N4P4F4(NMe2)4, N3P3F4(NHMe)2, N3PrF4(NHC4HS)2, or N3P3F4(NMe2)2. This behavior cannot be ascribed to steric effects because nuclcophiles such as CF3CH2ONa, C6H5ONa, and (CH3)2NLi readily replace all the fluorine atoms. The results are more compatible with an explanation based on the poor leaving-group ability of fluoride combined with the low nucleophilicity of the free amines, compared with the higherleaving-group ability of chloride and the high nucleophilicity of alkoxides, aryl oxides, or metal amides.

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ER -

The Partial Aminolysis of (NPF₂)_{3, 4}

Abstract

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