Conformations of diphosphinoamines; variable-temperature nuclear magnetic resonance and X-ray crystallographic studies

Keat, R., Manojlović-Muir, L., Muir, K. W. and Rycroft, D. S. (1981) Conformations of diphosphinoamines; variable-temperature nuclear magnetic resonance and X-ray crystallographic studies. Journal of the Chemical Society: Dalton Transactions, 1981(11), pp. 2192-2198. (doi:10.1039/DT9810002192)

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Abstract

The variable-temperature 31P-{1H} n.m.r. spectra of a series of diphosphinoamines, X2PN(R)PX2(R = H, Me, Et, or Pri, X = Ph; R = Me, But, or CH2But, X = Cl; R = Me or But, X = F; R = Et, X = NMe2) have been studied. Complementary information on these compounds has been obtained from 1H, 13C, and 19F n.m.r., including double and triple resonance experiments. The coupling constant, 2J(PNP), covers the range –23.9 to 731.9 Hz, and its magnitude and sign can be related to the proportion of molecules in which the local symmetry of the P–N–P skeleton is C2v rather than Cs. Diphosphinoamine conformers of the latter type have been clearly identified for the first time both in solution (for R = Et or Pri, X = Ph, and R = But or CH2But, X = Cl) and also in the solid phase. X-Ray analysis of Ph2PN(Pri)PPh2, based on 1 269 diffractometric intensities refined to R = 0.035, shows that the symmetry of the P–N–P skeleton is close to Cs in the solid, with P–N = 1.706(4) and 1.711(4) Å, and PNP = 122.8(3)°.

Item Type:Articles
Keywords:NMR spectroscopy, phosphorus chemistry.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Muir, Dr Kenneth and Rycroft, Dr David
Authors: Keat, R., Manojlović-Muir, L., Muir, K. W., and Rycroft, D. S.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the Chemical Society: Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN:0300-9246

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