Abstract
It has been previously reported that dimeric compounds of the general formula [L3Cu(II)]2(μ-Cl)2 exhibit a correlation between their magnetic coupling constantJ and the bridging Cu-Cl-Cu angle. A full survey of the published structural and magnetic data on these compounds confirms this correlation but leads to the conclusion that its physical significance is questionable. EHMO calculations on Cu2Cl 4−8 and its bromo analog show that the molecular orbitals responsible for the magnetic behavior of the dimers are not the orbitals responsible for the bonding interactions in these dimers. Therefore, they are very weakly affected by variations of the molecular structure, and no significant correlation betweenJ and any of the structural parameters is theoretically predicted. However, this situation changes when the coordination around the Cu atoms is strongly and dissymmetrically pyramidalized.
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Alemany, P., and Alvarez, S. (1990)Chem. Mater. 2, 723.
Ammeter, J. M., Bürgi, H. B., Thibeault, J. C., and Hoffmann, R. (1978)J. Am. Chem. Soc. 100, 3686.
Bencini, A., and Gatteschi, D. (1986)J. Am. Chem. Soc. 108, 5763.
Carrabine, J. A., and Sundaralingam, M. J. (1970)J. Am. Chem. Soc. 92, 369.
Crawford, V. H., Richardson, H. W., Wasson, J., Hodgson, D. J., and Hatfield, W. E. (1976)Inorg. Chem. 15, 2107.
Charlot, M. F., Verdaguer, M. Journaux, Y., de Loth, P., and Daudey, P. (1984)Inorg. Chem. 23, 3804.
Chiari, B., Piovesana, O., Tarantelli, T., and Zanazzi, P. F. (1989)Inorg. Chem. 28, 2141.
Daudey, J. P., de Loth, P., and Malrieu, J. P. (1985) InMagnetostructural correlations in exchange coupled systems. Willet, R. D.et al. (eds.), Reidel, D. Publishing Company, pp. 87–104.
Declerq, J. P., Debbaudt, M., and Van Meerssche, M. (1971)Bull. Soc. Chim. Belg. 61, 287.
Drake, R. F., Crawford, V. H., Laney N. W., Hatfield, W. E., and Hodgson, D. J. (1974)Inorg. Chem. 20, 1246.
Elian, M., and Hoffmann, R. (1975)Inorg. Chem. 14, 1058.
Endres, H. (1978)Acta Crystallogr. B 34, 3736.
Estes, W. E. (1977) Ph. Dissertation. The University of North Carolina, Chapel Hill.
Estes, E. D., Estes, W. E., Hatfield, W. E., and Hodgson, D. J. (1975)Inorg. Chem. 14, 106.
Fackler, J. Personal communication.
Fletcher, R., Hansen, J. J., Livermore, J., and Willet, R. D. (1983)Inorg. Chem. 22, 330.
Garland, M. T., Grandjean, D., Spodine, E., and Manzur, J. (1987)Acta Crystallogr. C 43, 643.
Hatfield, W. E. InMagneto-structural correlations in exchange coupled systems. R. D. Willeyet al. (eds.) Reidel Publishing Company, pp. 555–602.
Hay, P. J., Thibeault, J. C., and Hoffmann, R. (1975)J. Am. Chem. Soc. 97, 4884.
Hodgson, D. J. (1975)Prog. Inorg. Chem. 19, 173.
Hodgson, D. J., Hale, P. K., and Hatfield, W. E. (1971)Inorg. Chem. 10, 1061.
Hoffmann, R. (1963)J. Chem. Phys. 39, 1397.
Hoffmann, R., and Lipscomb, W. N. (1962a),J. Chem. Phys. 36, 2179.
Hoffmann, R., and Lipscomb, W. N. (1962b),J. Chem. Phys. 36, 2179.
Hoffmann, R., and Lipscomb, W. N. (1962c),J. Chem. Phys. 36, 3489.
Hoffmann, R., and Lipscomb, W. N. (1962d),J. Chem. Phys. 37, 2872.
Hoffmann, D. J., Towle, D. K., Hatfield, W. E., Chadhuri, P., and Weinghard, K. (1984)Mol. Cryst. Liq. 107, 161.
Hoffmann, S. K., Towle, D. K., Hatfield, W. E., Chadhuri, P., and Weinghardt, K. (1985)Inorg. Chem. 24, 1307.
Jeter, D. Y., Hodgson, D. J., and Hatfield, W. E. (1971)Inorg. Chim. Acta 5, 257.
Jounaux, D. Y., and Kahn, O. (1979)J. C. S. Dalton, 1575.
Kahn, O. (1984)Comment Inorg. Chem. 3, 105.
Kahn, O. (1986) InThe challenge of transition metals and coordination chemistry. Quantum Chemistry, A. Veillard (ed.), Reidel, D. Publishing Company, pp. 403–412.
Kahn, O., and Briat, B. J. (1976)Chem. Soc. Faraday Trans. 286, 1441.
Kahn, O., and Charlot, M. F. (1980)Nouv. J. Chem. 4, 567.
Landee, C. P., and Greeney, R. E. (1986)Inorg. Chem. 25, 3771.
de Looth, P. Cassoux, P., Daudey, J. P., and Malrieu, J. P. (1981)J. Am. Chem. Soc. 103, 4007.
Luukkonen, E., and Pajunen, A. (1973)Suomen Kemist B 46, 292.
Marsh, W. E. (1982b). Ph. Dissertation. The University of Chapel Hill, North Carolina.
Marsh, W. E., Bowman, T. L., Harris, C. S., Hatfield, W. E., and Hodgson, D. J. (1981)Inorg. Chem. 20, 3864.
Marsh, W. E., Hatfield, W. E., and Hodgson, D. J. (1982)Inorg. Chem. 21, 2679.
Marsh, W. E., Bowman, T. L., Hatfield, W. E., and Hodgson, D. J. (1982)Inorg. Chim. Acta 59, 19.
Marsh, W. E., Patel, K. C., Hatfield, W. E., and Hodgson, D. J. (1985)Inorg. Chem. 22, 511.
McGregor, K. T., Losse, D. B., Hodgson, D. J., and Hatfield, W. E. (1974)Inorg. Chem. 13, 756.
Megnamisi-Belome, M., and Novotny, M. A. (1980)Inorg. Chem. 19, 2470.
Phelps, D. W., Goodman, W. H., and Hodgson, D. J. (1976)Inorg. Chem. 15, 2266.
Roxy, B. W., Hatfield, W. E., and Hodgson, D. J. (1976)Inorg. Chem. 15, 1712.
Singh, P., Jeter, D. Y., Hatfield, W. E., and Hodgson, D. J. (1972)Inorg. Chem. 11, 1657.
Spodine, E., Manzur, J., Peña, O., and Garland, M. T. (1986)Bol. Soc. Quim. 31, (13), 109.
Sudaralingam, M., and Carrabine, J. A. (1971)J. Mol. Biol. 61, 287.
Svedung, D. V. (1965)Acta Chem. Scand. 23, 2865.
Swank, D. D., Needham, G. F., and Willet, R. D. (1979)Inorg. Chem. 18, 761.
Towle, D. K., Hoffmann, S. K., Hatfield, W. E., Singh, P., Chaudhuri, P., and Wieghard, K. (1985)Inorg. Chem. 24, 4393.
Van Kalkeren, G., Schmidt, W. W., and Block R. (1979)Physica 978, 315.
Walking, N. T., Dixon, E. E., Crawford, V. H. McGregor, K. T., and Hatfield, W. E. J. (1973)J. Chem. Soc. Chem. Commun. 133.
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Garland, M.T., Saillard, J.Y. & Spodine, E. Structure, bonding, and magnetic behavior of bis(μ-chloro)-and (μ-bromo)-bridged Cu(II) dimers. Journal of Crystallographic and Spectroscopic Research 22, 467–475 (1992). https://doi.org/10.1007/BF01195409
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DOI: https://doi.org/10.1007/BF01195409