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Structure and dissociation of ylidyl chlorophosphanes

Structure and dissociation of ylidyl chlorophosphanes The ylidyl substituent of the chlorophosphane Ph3P(DOUBLE BOND)CAr(SINGLE BOND)PRCl exerts a strong influence on the P(SINGLE BOND)Cl bond. An X‐ray structure investigation of the representative with Ar(DOUBLE BOND)Ph, R(DOUBLE BOND)Me reveals the longest P(SINGLE BOND)Cl bond ever observed for an acyclic chlorophosphine (226.2(1) pm). It is connected to a conformation that allows an effective negative hyperconjugation. The ylidyl chlorophosphanes with an amino group R are covalent in benzene but become more or less ionic in dichloromethane solution. The solvent‐dependent dissociation equilibrium can be followed by 31P NMR spectra. In case of an enamine‐derived ylidyl chlorophosphane, the equilibrium shifts almost completely from the covalent to the ionic side within a rather narrow range of solvent composition (20 to 70 vol % dichloromethane). © 1996 John Wiley & Sons, Inc. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Heteroatom Chemistry Wiley

Structure and dissociation of ylidyl chlorophosphanes

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References (19)

Publisher
Wiley
Copyright
Copyright © 1996 John Wiley & Sons, Inc.
ISSN
1042-7163
eISSN
1098-1071
DOI
10.1002/(SICI)1098-1071(199608)7:4<239::AID-HC5>3.0.CO;2-0
Publisher site
See Article on Publisher Site

Abstract

The ylidyl substituent of the chlorophosphane Ph3P(DOUBLE BOND)CAr(SINGLE BOND)PRCl exerts a strong influence on the P(SINGLE BOND)Cl bond. An X‐ray structure investigation of the representative with Ar(DOUBLE BOND)Ph, R(DOUBLE BOND)Me reveals the longest P(SINGLE BOND)Cl bond ever observed for an acyclic chlorophosphine (226.2(1) pm). It is connected to a conformation that allows an effective negative hyperconjugation. The ylidyl chlorophosphanes with an amino group R are covalent in benzene but become more or less ionic in dichloromethane solution. The solvent‐dependent dissociation equilibrium can be followed by 31P NMR spectra. In case of an enamine‐derived ylidyl chlorophosphane, the equilibrium shifts almost completely from the covalent to the ionic side within a rather narrow range of solvent composition (20 to 70 vol % dichloromethane). © 1996 John Wiley & Sons, Inc.

Journal

Heteroatom ChemistryWiley

Published: Jan 1, 1996

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