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Original Articles

DETERMINATION OF THE NATURE OF THE CONFORMATIONAL TRANSMISSION EFFECT IN PENTACOORDINATED PHOSPHORUS COMPOUNDS

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Pages 73-80 | Received 30 Jun 1986, Published online: 03 Jan 2007

References

  • Koole , L. H. , Lanters , E. J. and Buck , H. M. 1984 . J. Am. Chem. Soc. , 106 : 5451
  • Meulendijks , G. H. W. M. , van Es , W. , de Haan , J. W. and Buck , H. M. 1986 . Eur. J. Biochem. , 157 : 421
  • de Vries , N. K. and Buck , H. M. 1986 . Red. Trav. Chim. Pays-Bos , 105 : 150
  • Haasnoot , C. A. G. , de Leeuw , F. A. A. M. and Altona , C. 1980 . Tetrahedron , 36 : 2783 The equation used is: where Δχ i = Δχ i − 0.24 ∑j Δχ j is the group electronegativity corrected for β-substituents. ϕ is the proton-proton torsion angle (taken as ±60° or 180°), and ζ i is a substituent orientation parameter. The electronegativity of the elements relative to hydrogen has been derived from the Huggins scale: Δχ0 = 1.30,Δχ N = 0.85, and Δχ C = 0.40. As the coordination of phosphorus is an effect in γ-substituents only, it does not affect the calculated coupling constants, which can therefore be used for both PIV and PV TBP compounds
  • Using 32K points and a spectral window of 3000 Hz, one obtains an accuracy of 0.09 Hz in coupling constants, resulting in population fractions with an accuracy of ca. 0.02. For the variable temperature experiments described later, 16K points were used with a spectral window of 300 Hz, yielding an accuracy of 0.018 Hz in coupling constants and 0.005 in population fractions
  • Wolfe , S. 1972 . Acc. Chem. Res. , 5 : 102
  • Kirby , A. J. 1983 . The Anomeric Effect and Related Stereoelectronic Effects at Oxygen , 32 – 36 . Berlin : Springer Verlag .
  • Scheffers-Sap , M. M. E. and Buck , H. M. 1980 . J. Am. Chem. Soc. , 102 : 6422
  • Aldrich , H. S. , Alworth , L. A. and Clement , N. R. 1978 . J. Am. Chem. Soc. , 100 : 2362
  • Lehn , J.-M. and Wipff , G. 1976 . J. Am. Chem. Soc. , 98 : 7498
  • Luckenbach , R. 1973 . Dynamic Stereochemistry of Pentacoordinated Phosphorus and Related Elements , 3 – 5 . Stuttgart : Georg Thieme Verlag .
  • Dynamic Stereochemistry of Pentacoordinated Phosphorus and Related Elements 10 – 11 .
  • Ramirez , F. 1968 . Acc. Chem. Res. , 1 : 168 See for instance
  • Gorenstein , D. and Westheimer , F. H. 1970 . J. Am. Chem. Soc. , 92 : 634
  • Measurements of JPOMe were performed with 32K points and a spectral window of 100 Hz, giving an accuracy of 0.003 Hz in coupling constants. Repeated measurements showed the coupling constants to be reproducible within 0.01 Hz
  • 43 – 46 . 50 – 51 . Reference 8
  • Janssen , R. A. J. , Visser , G. J. and Buck , H. M. 1984 . J. Am. Chem. Soc. , 106 : 3429 Although the MNDO method does not include d-orbitals for phosphorus in its parametrization, a fifth bond can be accommodated because the program uses four bonding MOs and the first antibonding MO. In the latter MO, the AO of phosphorus has the same symmetry as the necessary d-orbital. This is shown by MNDO calculations on PH5, and is confirmed by earlier ab initio work on the same molecule
  • Powell , M. J. D. 1968 . A FORTRAN Subroutine for Solving Systems of Non-linear Algebraic Equations Harvell Report, AERE-R5947, H.M.S.O.
  • PANIC program , Switzerland : Bruker Spectrospin AG . copyright
  • Ramirez , F. 1966 . Bull. Soc. Chim. Fr. , 1 : 2443

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