Nuclear magnetic resonance investigation of rotation about phosphorus(V)–nitrogen bonds in aminocyclodiphosph(V)azanes

Keat, R., Rycroft, D. S. and Thompson, D. G. (1980) Nuclear magnetic resonance investigation of rotation about phosphorus(V)–nitrogen bonds in aminocyclodiphosph(V)azanes. Journal of the Chemical Society: Dalton Transactions, 1980(10), pp. 1858-1862. (doi:10.1039/DT9800001858)

Full text not currently available from Enlighten.

Abstract

Hydrogen-1 n.m.r. data on the cyclodiphosph(V)azanes [R2N(X)PNBut]2 (R = Me, X = O, S, or Se; R = Et, X = S or Se) and [Me2N(O)PNR]2 (R = Ph or CH2Ph) indicate that rotation about the exo PV–N bonds is slow on the n.m.r. time scale at ambient or sub-ambient temperatures. In the former series, trans isomers have higher rotational barriers, ΔGTc, than analogous cis isomers and these barriers are also greater for trans oxides than analogous sulphides or selenides. The rotational barriers for PV–N and PIII–N have also been measured for the compounds Me2NP[NBut]2P(X)NMe2 (X = S, Se, or MeI), Me2N(X)P[NBut]2P(Y)Cl (X = S, Y = lone pair; X = O, Y = O), and cis-Me2N(S)P[NBut]2P(Se)NMe2. Carbon-13 n.m.r. data obtained at various temperatures on geometrical isomers of [Me2N(X)PNBut]2 (X = O, S, or Se) indicate that J(PNC) (exo) is much more stereospecific than J(PNCH), especially when X = S or Se.

Item Type:Articles
Keywords:Phosphorus chemistry, NMR spectroscopy.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Rycroft, Dr David
Authors: Keat, R., Rycroft, D. S., and Thompson, D. G.
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:The Royal Society of Chemistry
ISSN:0300-9246

University Staff: Request a correction | Enlighten Editors: Update this record