Abstract
CONSIDERABLE interest has recently been shown in steric effects in simple octahedral complexes. Gloneck, Curran and Quagliano1, for example, observed that the octahedral complexes NiX2B4 (X = a halogen, B = a heterocyclic base) could not be obtained with iodides or with 2-methylpyridine, the co-ordination number of the nickel then being restricted to four; analogous results have been obtained by Lever, Lewis and Nyholm for complexes of cobalt (II) halides with alkyl-substituted pyrazines2. Sacconi, Lombardo and Paoletti3 report entropies for the addition of bases to diacetylbis(benzoylhydrazone) nickel (II), which are significantly different for 2-methylpyridine, 2,6-dimethylpyridine and quinoline as compared with pyridine and 3- or 4-methylpyridine, and Graddon and Watton4 report equilibrium constants for the addition of bases to copper (II) β-diketone complexes increasing in the order 2,6-dimethylpyridine < 2-methylpyridine < pyridine < 4-methylpyridine; they also observe considerable solvent effects, indicating that chloroform should not be regarded as inert in reactions of this sort.
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References
Gloneck, M. D., Curran, C., and Quagliano, J. V., J. Amer. Chem. Soc., 84, 2014 (1962).
Lever, A. B. P., Lewis, J., and Nyholm, R. S., J. Chem. Soc., 1235 (1962).
Sacconi, L., Lombardo, G., and Paoletti, P., J. Chem. Soc., 848 (1958).
Graddon, D. P., and Watton, E. C., J. Inorg. Nucl. Chem., 21, 49 (1961).
King, H. C. A., Körös, E., and Nelson, S. M., Nature, 196, 572 (1962).
Dunitz, J. D., Acta Cryst., 10, 307 (1957).
Lippert, E. L., and Truter, M. R., J. Chem. Soc., 4996 (1960).
Bruehlmann, R. J., and Verhoek, F. H., J. Amer. Chem. Soc., 70, 1401 (1948).
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GRADDON, D., SCHULZ, R., WATTON, E. et al. Steric Effects in Simple Octahedral Complexes. Nature 198, 1299–1300 (1963). https://doi.org/10.1038/1981299a0
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DOI: https://doi.org/10.1038/1981299a0
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