Asymmetry in alkoxyfluorophosphoranes

SUMMARYWe present some properties of NMR first order spectra in relation with the permutational character of intramolecular rearrangements. We use the symmetry properties of the effective spin hamiltonian in order to analyse the KuboSack exchange matrices. In this context, we propose the experimental study of two molecules and we show that this study could give rise to new information about the permutational character of the rearrangements responsible for their non-rigidity. I. INTRODUCTIONIn connection with stereochemical nonrigidity the study of line-shapes of NMR spectra has appeared to be an exceptionally powerful method, as well for estimating the energy barrier, and more precisely the free enthalpy of activation of the rearrangements resulting from this nonriqidity as for determining their permutational character (see below) 2' 15-17. The theory of line-shape analysis in NMR and its application to chemical exchange have been extensively reviewed,and we refer the interested reader to the original papers for detai1~l-l~. The principle of NMR line-shape analysis lies on the use of a mathematical model that can be programmed. The data of this model, i.e. the input of the program,are experimental parameters such as chemical shifts, scalar coupling constants, line-widths (i.e. inverses of transverse relaxation times), and, last but not least, a given rate constant for the chemical exchange under study, and an operator, or set of operators, describing the permutational character of the rearrangemet~t~~' 5' 15-17. The output of the model is a theoretical NMR spectrum whose line-shapes depend not only on the rate of exchange of the nonrigid molecule, but also on the permutational character of the exchange under consideration. It is

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The Use of First Order NMR Spectra in Determining the Permutational Character of Intramolecular Rearrangements

Brocas

Buschen

Decoster

et al. 1977

Bulletin des Soc Chimique

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PHOSPHORUS-FLUORINE CHEMISTRY PART XLII¹. PYRROLE-SUBSTITUTED FLUOROPHOSPHORANES

Hewson

Schmutzler

1980

Phosphorus and Sulfur and the Related Elements

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Asymmetry in alkoxyfluorophosphoranes

Abstract: The apical fluorine atoms are shown to be convenient, sensitive n.m.r. probes for investigating the stereochemistry of alkoxyfluorophosphoranes of types (I)-(IV) having 1, 2, or 3 identical or different fastrotating asymmetric alkyl or alkoxy groups.

Cited by 2 publications

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The Use of First Order NMR Spectra in Determining the Permutational Character of Intramolecular Rearrangements

The Use of First Order NMR Spectra in Determining the Permutational Character of Intramolecular Rearrangements

PHOSPHORUS-FLUORINE CHEMISTRY PART XLII¹. PYRROLE-SUBSTITUTED FLUOROPHOSPHORANES

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Asymmetry in alkoxyfluorophosphoranes

Abstract: The apical fluorine atoms are shown to be convenient, sensitive n.m.r. probes for investigating the stereochemistry of alkoxyfluorophosphoranes of types (I)-(IV) having 1, 2, or 3 identical or different fastrotating asymmetric alkyl or alkoxy groups.

Cited by 2 publications

References 0 publications

The Use of First Order NMR Spectra in Determining the Permutational Character of Intramolecular Rearrangements

The Use of First Order NMR Spectra in Determining the Permutational Character of Intramolecular Rearrangements

PHOSPHORUS-FLUORINE CHEMISTRY PART XLII1. PYRROLE-SUBSTITUTED FLUOROPHOSPHORANES

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Product

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About

PHOSPHORUS-FLUORINE CHEMISTRY PART XLII¹. PYRROLE-SUBSTITUTED FLUOROPHOSPHORANES