You need JavaScript to view this

Contribution to the study of the {sup 31}P, {sup 1}H spin spin coupling constant N. M. R. in three co-ordinated phosphorus compounds. Influence of the bond orientation and of the nature of the substituent around the phosphorus atom; Contribution a l'etude des constantes de couplage {sup 31}P, {sup 1}H en R.M.N. dans les composes organo-phosphores tricoordines. Influence des facteurs geometriques et de la nature des substituants au niveau du phosphore

Abstract

In order to investigate the influence of the configuration at the phosphorus atom and the influence of the substituents attached to the phosphorus atom on the J{sub PH} spin spin coupling constant, we have performed the NMR spectrum analysis of some three coordinated organo-phosphorus compounds. The studied coupling constants are {sup 3}J{sub PH} through P-O-C-H and P-C-C-H fragments and {sup 2}J{sub PH} through P-C-H fragment. The results clearly show that on the NMR time scale, in all the studied compounds (1,3,2-dioxaphospholanes, 1,3,2-dioxaphosphorinanes, 3-phospha-cyclopentene and 4-phosphorinanone) there is no inversion of the bonds around phosphorous. This conclusion held also for secondary phosphines. For a given geometry of the bonds joining the P and H atoms, and a given disposition of the bonds around the phosphorus atom, there is only a little influence of the nature of the substituents on the J{sub PH} spin coupling constants. The geometrical dependence of the {sup 3}J{sub PH} cannot be explained by a 'Karplus law'. There is an influence of the bond disposition around phosphorus. In the case of the {sup 2}J{sub P-C-H}, one can plot a curve {sup 2}J{sub P-C-H} = f({alpha}) (0{<=} {alpha} {<=} 180), {alpha} denote the dihedral angle of the two plane  More>>
Authors:
Robert, J B [1] 
  1. Commissariat a l'Energie Atomique, Grenoble (France). Centre d'Etudes Nucleaires
Publication Date:
Jul 01, 1969
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-3671
Resource Relation:
Other Information: TH: These docteur ES-sciences; 196 refs; PBD: 1969
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; GEOMETRY; J-J COUPLING; NUCLEAR MAGNETIC RESONANCE; ORGANIC PHOSPHORUS COMPOUNDS; SPIN; STEREOCHEMISTRY
OSTI ID:
20528701
Research Organizations:
CEA Grenoble, 38 (France); Grenoble-1 Univ., Faculte des Sciences, 38 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR04R3671094967
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
[127] pages
Announcement Date:
Dec 10, 2004

Citation Formats

Robert, J B. Contribution to the study of the {sup 31}P, {sup 1}H spin spin coupling constant N. M. R. in three co-ordinated phosphorus compounds. Influence of the bond orientation and of the nature of the substituent around the phosphorus atom; Contribution a l'etude des constantes de couplage {sup 31}P, {sup 1}H en R.M.N. dans les composes organo-phosphores tricoordines. Influence des facteurs geometriques et de la nature des substituants au niveau du phosphore. France: N. p., 1969. Web.
Robert, J B. Contribution to the study of the {sup 31}P, {sup 1}H spin spin coupling constant N. M. R. in three co-ordinated phosphorus compounds. Influence of the bond orientation and of the nature of the substituent around the phosphorus atom; Contribution a l'etude des constantes de couplage {sup 31}P, {sup 1}H en R.M.N. dans les composes organo-phosphores tricoordines. Influence des facteurs geometriques et de la nature des substituants au niveau du phosphore. France.
Robert, J B. 1969. "Contribution to the study of the {sup 31}P, {sup 1}H spin spin coupling constant N. M. R. in three co-ordinated phosphorus compounds. Influence of the bond orientation and of the nature of the substituent around the phosphorus atom; Contribution a l'etude des constantes de couplage {sup 31}P, {sup 1}H en R.M.N. dans les composes organo-phosphores tricoordines. Influence des facteurs geometriques et de la nature des substituants au niveau du phosphore." France.
@misc{etde_20528701,
title = {Contribution to the study of the {sup 31}P, {sup 1}H spin spin coupling constant N. M. R. in three co-ordinated phosphorus compounds. Influence of the bond orientation and of the nature of the substituent around the phosphorus atom; Contribution a l'etude des constantes de couplage {sup 31}P, {sup 1}H en R.M.N. dans les composes organo-phosphores tricoordines. Influence des facteurs geometriques et de la nature des substituants au niveau du phosphore}
author = {Robert, J B}
abstractNote = {In order to investigate the influence of the configuration at the phosphorus atom and the influence of the substituents attached to the phosphorus atom on the J{sub PH} spin spin coupling constant, we have performed the NMR spectrum analysis of some three coordinated organo-phosphorus compounds. The studied coupling constants are {sup 3}J{sub PH} through P-O-C-H and P-C-C-H fragments and {sup 2}J{sub PH} through P-C-H fragment. The results clearly show that on the NMR time scale, in all the studied compounds (1,3,2-dioxaphospholanes, 1,3,2-dioxaphosphorinanes, 3-phospha-cyclopentene and 4-phosphorinanone) there is no inversion of the bonds around phosphorous. This conclusion held also for secondary phosphines. For a given geometry of the bonds joining the P and H atoms, and a given disposition of the bonds around the phosphorus atom, there is only a little influence of the nature of the substituents on the J{sub PH} spin coupling constants. The geometrical dependence of the {sup 3}J{sub PH} cannot be explained by a 'Karplus law'. There is an influence of the bond disposition around phosphorus. In the case of the {sup 2}J{sub P-C-H}, one can plot a curve {sup 2}J{sub P-C-H} = f({alpha}) (0{<=} {alpha} {<=} 180), {alpha} denote the dihedral angle of the two plane defined the first one by the P, C and H atoms, and the second one by the P-C bond together with the three-fold axis of the bond around phosphorus assuming a regular pyramidal arrangement. The function {sup 2}J{sub P-C-H} = f({alpha}) has two maxima, one for {alpha} = 0 degrees and the other for {alpha} = 180 degrees, and also a minimum for {alpha} = 110 degrees. (author) [French] Ce travail consiste en l'analyse par resonance magnetique nucleaire des constantes de couplage phosphore-proton dans des derives organo-phosphores tricoordines dans un double but: examen de la stabilite des liaisons au niveau du phosphore et etude de l'influence de la disposition des liaisons et de la nature de substituants au niveau du phosphore. Les constantes de couplage sont du type {sup 3}J{sub PH} au travers des fragments P-C-C-H et P-O-C-H, et {sup 2}J{sub PH} au travers du fragment P-CH. Les resultats montrent que, pour les temps d'observation de la RMN, la disposition des liaisons au niveau du phosphore dans l'ensemble des composes etudies (dioxaphospholanes-1,3,2, dioxaphosphorinanes-1,3,2, phosphacyclopentenes-3, phosphorinanones-4) qui portent des substituants varies au niveau du phosphore, est pyramidale et fixe. Ce resultat s'applique egalement aux phosphines secondaires. Le couplage depend tres peu des substituants fixes sur le phosphore sauf dans le cas d'un azote. Pour les couplages {sup 3}J, les resultats montrent que la dependance attendue, basee uniquement sur l'angle diedre de type ''Karplus'', ne suffit pas. La direction du doublet libre donne lieu a une variation supplementaire sur J. Dans le cas des couplages {sup 2}J{sub P-C-H} cette influence est le facteur principal, les variations de J allant de + 25 cps a -6 cps: les valeurs peuvent etre traduites par une loi J = f({alpha}) (0 {<=} {alpha} {<=} 180) {alpha} etant l'angle diedre des plans H-C-P et C-P-X, X representant la direction du doublet libre (axe ternaire de la pyramide passant par le phosphore). (auteur)}
place = {France}
year = {1969}
month = {Jul}
}