Abstract
A theoretical study on the conformation of allyl halides from the calculation of nuclear spin-spin coupling constants by adopting the finite perturbation theory (FPT), is carried out in terms of the self-consistent, semi-empirical INDO (intermediate neglect of differential overlap) approximation of molecular orbital theory. Results of the calculations performed using ‘s’ and ‘p’ valence orbitals alone (‘sp’ basis) at INDO level approximation seem to replicate the experimental trend quite satisfactorily. Despite the overall agreement of the theoretical values with the experimental ones, the uncertainties in the INDO parametrization scheme lead to overestimation of certain coupling constants. The calculations also show that the orientation of the coupled protons with respect to the substituent halogen atom is an important factor to be considered.
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References
Barfield M 1971J. Am. Chem. Soc. 93 5
Barfield M and Karplus M 1969J. Am. Chem. Soc. 91 1
Bingham R C, Dewar M J S and Lo D M 1975J. Am. Chem. Soc. 97 1285
Bothner-By A A, Castellano S and Gunther H 1965J. Am. Chem. Soc. 87 2439
Bothner-By A A, Castellano S and Gunther H 1966J. Am. Chem. Soc. 88 2466
Bothner-By A A and Gunther H 1962Disc. Faraday Soc. 34 127
Cadioli B and Pincelli U 1972J. Chem. Soc. Faraday Trans. 268 991
Contreras R H, Engelmann A R, Scuseria and Facelli J C 1980Org. Mag. Reson. 13 137
Dewar M J, Landman D, Such S H and Weiner P K 1977J. Am. Chem. Soc. 99 3951
Ewing D F and Parry K A W 1970J. Chem. Soc. (B) Part 1 970
Galasso V 1974Theor. Chim. Acta 34 137
Goodman B A and Raynor J B 1970 inAdvances in inorganic chemistry and radiochemistry (eds) H J Emeleus and A G Sharpe (New York: Academic Press)13
Govil G 1967Mol. Phys. 12 293
Halmann M, Laulicht I and Steinfeld J I 1966J. Mol. Spectrosc. 21 332
Hase H L and Schweig A 1973Theor. Chim. Acta 31 215
Helene Schei and Quang Shen 1982J. Mol. Struct. 81 269
Herschbach D R and Krisher L C 1958J. Chem. Phys. 28 728
Hirota E 1962Proc. Int. Symp. Mol. Struct. Spectrosc. (Tokyo) C402-1
Klib R W, Lin C C and Wilson E B 1957J. Chem. Phys. 26 1695
Kowalewski J 1977Progress in NMR spectroscopy (eds) J W Emsley, J Feeny and L H Sutcliffe (Oxford: Pergamon Press)2 1
Meinwald J and Lewis A 1961J. Am. Chem. Soc. 83 2769
Padwa A, Shefter E and Alexander E 1968J. Am. Chem. Soc. 90 3717
Pople J A and Beveridge D L 1970Approximate molecular orbital theory (New York: McGraw-Hill)
Pople J A, McIver J W and Ostlund N S 1966Chem. Phys. Lett 1 272
Pople J A, McIver J W and Ostlund N S 1968J. Chem. Phys. 49 2960, 2965
Ramsey N F 1953Phys. Rev. 91 303
Santhanam V and Sobhanadri J 1986Proc. Indian Acad. Sci (Chem. Sci.) 96 363
Sutton L E 1965Tables of inter-atomic distances (London: The Chemical Society)
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Santhanam, V., Sobhanadri, J. & Subramaniam, S. Conformational analysis of allyl halides from the calculation of indirect spin-spin coupling. Pramana - J Phys 30, 43–50 (1988). https://doi.org/10.1007/BF02875616
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DOI: https://doi.org/10.1007/BF02875616