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Nuclear Quadrupole Coupling in the Alkali Chloroiodides. I. Chlorine Resonances
1.L. Pauling, Nature of the Chemical Bond (Cornell University Press, Ithaca, 1940), pp. 92–93, 109–111,
2.J. H. Van Vleck and A. Sherman, Revs. Modern Phys. 7, 167 (1935), Sects. 21, 30;
2.G. Kimball, J. Chem. Phys. 8, 188 (1940),
2.Y. K. Syrkin and M. E. Dyatkina, Structure of Molecules (Butterworths Scientific Publications, London, 1950), p. 380,
2.T. Moeller, Inorganic Chemistry (John Wiley and Sons, Inc., New York, 1952), p. 445,
3.R. D. Burbank and F. N. Bensey, J. Chem. Phys. 21, 602 (1953),
4.R. C. L. Mooney, Z. Krist. 98, 377 (1938),
4.H. S. Gutowsky and C. J. Hoffman, J. Chem. Phys. 19, 1259 (1951),
4.Gordy, Smith, and Trambarulo, Microwave Spectroscopy (John Wiley and Sons, Inc., New York, 1953), p. 321,
4.Robinson, Dehmelt, and Gordy, J. Chem. Phys. 22, 515 (1954),
4.K. H. Boswijk and E. H. Wiebenga, Acta Cryst. 7, 417 (1954), See also reference 3, in which the possibility of π bonding via chlorine d orbitals is considered; the resulting polarity is different in character and in direction from the ionicity of σ bonds to which we refer.
5.R. J. Hach and R. E. Rundle, J. Am. Chem. Soc. 73, 4321 (1951),
6.G. C. Pimentel, J. Chem. Phys. 19, 446 (1951).
7.Data submitted to X‐ray Powder Data File, G. W. Brindley, Editor, Department of Ceramic Technology, The Pennsylvania State University, University Park, Pennsylvania.
8.Wells, Wheeler, and Penfield, Am. J. Sci. 43, 17, 475 (1892).
9.Wells, Wheeler, and Penfield, Am. J. Sci. 44, 42 (1892).
10.Kindly supplied by Professor Paul Bender. For preparation see P. Bender and R. A. Strehlow, J. Am. Chem. Soc. 70, 1995 (1948).
11.Swanson, Fuyat, and Ugrinic, Standard X‐Ray Diffraction Patterns, Natl. Bur. Standards Circ. 539 (U.S. Government Printing Office, Washington, 1954), Vol. III, p. 50.
12.R. W. G. Wyckoff, J. Am. Chem. Soc. 42, 1100 (1920).
13.We are indebted to Dr. H. C. Allen, Jr., and Dr. H. C. Meal for information on the design of their spectrometer, which is similar to that of Dean and Pound. See C. Dean, Ph.D. thesis, Harvard University (1952).
14.J. D. Graybeal and C. D. Cornwell (to be published).
15.R. B. Scott, in American Institute of Physics, Temperature, Its Measurement and Control in Science and Industry (Reinhold Publishing Corporation, New York, 1941), p. 206.
16.G. T. Armstrong, J. Research Natl. Bur. Standards 53, 263 (1954).
17.H. Krüger, Z. Physik 130, 371 (1951).
18.C. H. Townes and B. P. Dailey, J. Chem. Phys. 17, 782 (1949);
18.C. H. Townes and B. P. Dailey, 20, 35 (1952); , J. Chem. Phys.
18.B. P. Dailey and C. H. Townes, J. Chem. Phys. 23, 118 (1955).
18.For a general discussion see C. H. Townes and A. L. Schawlow, Microwave Spectroscopy (McGraw‐Hill Book Company, Inc., New York, 1955), Chap. 9.
19. frequencies are not included in this average.
20.The structure of the ion obtained by Mooney (reference 4) is assumed to be essentially correct because scattering due to water would not be large compared with the uncertainties in the estimated intensities.
21.G. L. Clark, Proc. Natl. Acad. Sci. U.S. 9, 117 (1923),
21.and G. L. Clark and W. Duane, J. Opt. Soc. Am. 7, 455 (1923),
21.R. C. L. Mooney, Z. Krist. 90, 143 (1935),
21.R. C. L. Mooney, Z. Krist. 98, 324 (1938),
21.R. C. L. Mooney, Z. Krist. 100, 519 (1939),
21.R. C. L. Mooney, Phys. Rev. 53, 851 (1938),
21.W. F. Zelezny and N. C. Baenziger, J. Am. Chem. Soc. 74, 6151 (1952),
22.Hach and Rundle (reference 5) employed similar structures for in their discussion of structures of polyiodide ions in crystals, but they specifically excluded the dichloroiodide ion from this treatment.
23.We interpret the interhalogen data in terms of the I‐Cl bond in ICl, whatever its nature, as common denominator, with the understanding that a further analysis of this bond in terms of sp hybridization and ionic character of the general magnitudes suggested by Townes et al. in reference 18 is appropriate. The coupling constant, which we associate with the symbol I‐Cl then corresponds, say, to 15% s hybridization of the chlorine bonding orbital and 15–30% ionic character.
24.Boswijk and Wiebenga (reference 4) also have suggested hybrid structures of this sort as being consistent with the observed interatomic distances, but they regarded the part of this structure as being formed from hybrid orbitals of iodine. The latter assumption is not implied in our analysis of this ion.
25.P. J. Bray, J. Chem. Phys. 23, 703 (1955).
26.Because of a difference in relative intensity (signal‐to‐noise ratios of and respectively, as above) Bray attributed the two observed resonances to the end and bridging chlorine atoms. However, the crystal structure (reference 4) is such that the molecule has a center of symmetry, but no other element, so the terminal atoms fall into two sets differing slightly in crystalline environment. We believe that the observed resonances arise from these two sets of atoms and that the resonances due to the bridging atoms have not been observed.
27.A discussion of these rules and their application to polyvalency in halogens is given by Van Vleck and Sherman (reference 2). See also Pauling (reference 1, pp. 30–33). These authors make clear the restriction to covalent bonding.
28.Examples of most of these may be found in references 3, 4, 12, 21. We know of no instance of six‐coordination in polyhalides which has been established by a structural determination, but is known and is expected to represent the octahedral arrangement. See H. J. Emeléus and A. G. Sharpe, J. Chem. Soc. 1949, 2206.
28.The tetrahedral structure reported for [S. Siegel, Acta Cryst. 9, 493 (1956)] seems inconsistent with the other polyhalide structures and is difficult to understand with or without d orbitals.
28.It seems wiser not to attempt to discuss [Lord, Lynch, Schumb, and Slowinski, J. Am. Chem. Soc. 72, 522 (1950)] until additional structural details are known.
29.R. M. Sternheimer, Phys. Rev. 105, 158 (1957), and earlier papers.
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