Three-Dimensional Macrocyclic Encapsulation Reactions. III.1,2 Geometrical and Electronic Features of Tris(diimine) Complexes of Trigonal-Prismatic, Antiprismatic, and Intermediate Stereochemistry

Inorganic Chemistry

Volumn 11, Issue 11, 1972, Pages 2652-2668

  Larsen, E ^a   La Mar, G N ^a   Wagner, B E ^a   Parks, J E ^a   Holm, R H ^a  

^a NONE

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Indexed keywords

EID: 33947091671     PISSN: 00201669     EISSN: 1520510X     Source Type: Journal    
DOI: 10.1021/ic50117a019     Document Type: Article

References (90)

1. Part I: J. E. Parks, B. E. Wagner, and R. H. Holm, J. Amer. Chem. Soc., 92, 3500 (1970).
2. Part II: J. E. Parks, B. E. Wagner, and R. H. Holm, Inorg, Chem., 10, 2472 (1971).
3. NATO Postdoctoral Fellow, 1970-1971.
4. R. Eisenberg, Progr. Inorg, Chem., 12, 295 (1970).
5. C. G. Pierpont and R. Eisenberg, J. Chem. Soc. A, 2285 (1971).
6. J. P. R. de Villiers and J. C. A. Boeyens, Acta Crystallogr., Sect. B, 28, 2335 (1971)
7. J. A. Bertrand, J. A. Kelly, and E. G. Vassian, J. Amer. Chem. Soc., 91, 2394 (1969).
8. T. A. Hamor and D. J. Watkin, Chem. Commun., 440 (1969);
9. S. Merlino, Acta Crystallogr., Sect. B, 24, 1441 (1968);
10. B. F. Hoskins and B. P. Kelly, Chem. Commun., 1517 (1968);
11. A. Avdeef, J. P. Fackler, Jr., and R. G. Fischer, Jr., J. Amer. Chem, Soc., 92, 6972 (1970);
12. D. L. Johnston, W. L. Rohrbaugh, and W. D. Horrocks, Jr., Inorg. Chem., 10, 1474 (1971);.
13. P. C. Healy and A. H. White, Chem. Commun., 1446 (1971);
14. S. Merlino, Acta Crystallogr., Sect. B, 25, 2270 (1969);
15. S. Merlino and F. Sartori, Acta Crystallogr., Sect. B, 28, 972 (1972);
16. B. F. Hoskins and B. P. Kelly, Chem. Commun., 45 (1970);
17. see also E. I. Stiefel and G. F. Brown, Inorg. Chem., 11, 434 (1972):
18. D. H. Busch, Ree. Chem. Progr., 25, 107 (1964).
19. M. R. Churchill and A. H. Reis, Jr., Chem. Commun., 879 (1970);
20. Inorg. Chem., 11, 1811 (1972);
21. M. R. Churchill and A. H. Reis, Jr., Chem. Commun., 1307 (1971);
22. Inorg. Chem., in press;
23. M. R. Churchill and A. H. Reis, Jr., results to be published.
24. W. O. Gillum, R. A. D. Wentworth, and R. F. Childers, Inorg. Chem., 9, 1825.(1970).
25. D. R. Boston and N. J. Rose, J. Amer. Chem. Soc., 90, 6859 (1968);
26. D. R. Boston and N. J. Rose, Abstracts, 157th National Meeting of the American Chemical Society, April 1969, No. INOR 96.
27. G. A., Zakrewski, C. A. Ghilardi, and E. C. Lingafelter, J. Amer. Chem. Soc., 93, 4411 (1971).
28. F. Lions and K. V. Martin, J. Amer. Chem. Soc., 79, 1572 (1957).
29. J. E. Sarneski and F. L. Urbach, Chem. Commun., 1025 (1968).
30. W. O. Gillum, J. C. Huffman, W. E. Streib, and R. A. D. Wentworth, Chem. Commun., 843 (1969).
31. E. B. Fleischer, A. E. Gebala, and D. R. Swift, Chem. Commun., 1280 (1971).
32. D. A. Durham, F. A. Hart, and D. Shaw, J. Inorg. Nucl. Chem., 29, 509 (1967).
33. F. P. Dwyer, N. S. Gill, E. C. Gyarfas, and F. Lions, J. Amer. Chem. Soc., 79, 1269 (1957).
34. E. B. Fleischer, A. E. Gebala, and P. Tasker, J. Amer. Chem. Soc., 92, 6365 (1970);
35. E. B. Fleischer, A. E. Gebala, D. R. Swift, and P. A. Tasker, Inorg. Chem., 11, 2775 (1972).
36. L. F. Urbach and S. O. Wandiga, Chem. Commun., 1572 (1970).
37. For a recent study of [M((py)3tame)]2 +, s + complexes see S. O. Waridiga, J. E. Sarneski, and F. L. Urbach, Inorg. Chem., 11, 1349 (1972).
38. L. J. Wilson and N. J. Rose, Abstracts, 158th National Meeting of the American Chemical Society, Sept 1969, No. INOR 89;
39. N. J. Rose, private communication;
40. L. J. Wilson and N. J. Rose, J. Amer. Chem. Soc., 90, 6041 (1968).
41. C. Mealli and E. C. Lingafelter, Chem. Commun., 885 (1978);
42. E. C. Lingafelter, private communication.
43. E. B. Fleischer, A. E. Gebala, A. Levey, and P. A. Tasker, J. Org. Chem., 36, 3042 (1971).
44. R. A. D. Wentworth and J. J. Felton, J. Amer. Chem. Soc., 90, 621 (1968).
45. H. Stetter and W. Böckman, Chem. Ber., 84, 834 (1951).
46. S. Ginsberg and I. B. Wilson, J. Amer Chem. Soc., 79, 481 (1957).
47. F. H. Burstall, J. Chem. Soc., 1662 (1938).
48. H. J. Jakobsen, J. Mol. Spectrosc., 34, 245 (1970).
49. E. Plaiek and R. Tyka, Zesz. Nauk. Politech. Wroclaw., Chem., No. 4, 79 (1957);
50. Chem. Abstr, 52, 20156c (1958).
51. G.A.R. Kon and H. R. Nangi, J. Chem. Soc. 560 (1931);
52. D. E. Ames, R. E. Bowman, and T. F. Grey, J. Chem. Soc., 3008 (1953);
53. H. Rogerson and J. F. Thorpe, J. Chem. Soc., 87, 1689 (1905);
54. D. E. Ames and T. F. Grey, J. Chem. Soc., 631 (1951).
55. C. E. Schaffer, Struct. Bonding {Berlin), 5, 68 (1968).
56. A. A. G. Tomlinson, J. Chem. Soc. A, 1409 (1971).
57. C. E. Schäffer and C. K. Jorgensen, Mol. Phys., 9, 401 (1965);
58. C. E. Schäffer, Proc. Roy. Soc., Ser. A, 297, 96 (1967).
59. E. C. Lingafelter and R. L. Braun, J. Amer. Chem. Soc., 88, 2951 (1966).
60. In a series of alkali metal cryptate complexes the twist angles increase in the order B. Metz, D. Moras, and R. Weiss, Chem. Commun., 444 (1971). The structures are intermediate between a bicapped TP and bicapped TAP. However, the M-O distances are not necessarily optimal due to the size of the OeN2 cage.
61. R. A. Palmer and T. S. Piper, Inorg, Chem., 5, 864 (1966).
62. M. A. Robinson, J. D. Curry, and D. H. Busch, Inorg, Chem., 2, 1178 (1963).
63. Y. Tanabe and S. Sugano, J. Phys. Soc. Jap., 9, 753, 766 (1954).
64. The data for this complex are in close agreement with the spectral results for [Ni(N(py)i)2](C10)2: G. C. Kulasingam, J. C. Lancaster, W. R. McWhinnie, and J. B. Watts, Spectrochim. Acta, Part A, 26, 835 (1970);
65. W. R. McWhinnie, G. S. Kulasingam, and J. C. Draper, J. Chem. Soc. A, 1199 (1966).
66. M. Ciampolini, Inorg. Chem., S, 35 (1966);
67. J. S. Wood, Inorg. Chem., S, 7, 852 (1968).
68. P. H. Davis and J. S. Wood, Chem. Phys. Lett., 4, 466 (1969).
69. This statement refers only to the series oí complexes under consideration. Other Ni-Ns TAP complexes with diimine-type ligands can have larger extinction coefficients. As one example, bis(2, 6-diacetylpyridyl∼ dioximo)nickel(II) has e ∼30 for its octahedral vj band: E. I. Baucom and R. S. Drago, J. Amer. Chem. Soc., 93, 6469 (1971).
70. Electrolysis at -0.5 V vs. see (cf. Table V) caused a marked increase in the intensities of these features. Spectral measurement of a solution subjected to prolonged reductive electrolysis indicated that the sample whose spectrum is shown in Figure 7 contained ca. 0.6% of the Co(I) complex. Electrochemical oxidation failed to remove completely this material. Its presence in all samples of the Co(II) salt which we have prepared led to inconclusive results in single-crystal polarized spectral measurements. Additional experiments using acetonitrile solutions indicated that the Co (I) complex could also be generated photolytically, as appears to be the case for [Co(bipy)3]2+.40 The shoulder at ∼16, 000 cm”1 in the spectrum of [Co-(bipy)a]2 + in Figure 9 and in that reported earlier40 coincides with the 16, 400-cm”1 band of [Co(bipy)g] + (Y. Kaizu, Y. Tórii, and H. Kobayashi, Bull. Chem. Soc. Jap., 43, 3296 (1970)). An additional band of the latter at 7200 cm-1 was not detected, however. Bands suspected to be due to Co(I) impurities in other complexes are so designated in Figures 7 and 9 and in Table III.
71. D. R. Eaton and W. D. Phillips, Advan. Magn. Resonance, 1, 103 (1965);
72. R. H. Holm, Accounts Chem. Res., 2, 307 (1969);
73. G. N. La Mar and L. Sacconi, J. Amer. Chem. Soc., 89, 2282 (1967).
74. M. Wicholas and R. S. Drago, J. Amer. Chem. Soc., 90, 6946 (1968). Differences in solvent between this work and ours produce small changes in line widths and shifts. The 6, 6'-H signal could not be located with the concentrations employed in the present study.
75. J. A. Happe and R. L. Ward J. Chem. Phys., 39, 1211 (1963);
76. R. H. Holm, G. W. Everett, Jr., and W. D. Horrocks, Jr., J. Amer. Chem. Soc., 88, 1071 (1966);
77. W. D. Horrocks, Jr., and D. L. Johnston, Inorg. Chem., 10, 1835 (1971).
78. J. P. Jesson, J. Chem. Phys., 47, 582 (1967);
79. W. D. Horrocks, Jr., Inorg. Chem., 9, 690 (1970).
80. I. Solomon, Phys. Rev., 99, 559 (1955);
81. N. Bloembergen, J. Chem. Phys., 27, 572 (1955).
82. R. A. Bernheim, T. H. Brown, H. S. Gutowsky, and D. E. Woessner, J. Chem. Phys., 30, 950 (1959).
83. N. Bloembergen and L. O. Morgan, J. Chem. Phys., 34, 842 (1961);
84. W. B. Lewis and L. O. Morgan, Transition Metal Chem., 4, 33 (1968).
85. C. J. Ballhausen, “Introduction to Ligand Field Theory,” McGraw-Hill, New York, N. Y., 1962, pp 134-135.
86. G. N. LaMar and G. R. Van Hecke, J. Chem. Phys., 52, 5676 (1970).
87. B. Martin, W. R. McWhinnie, and G. M. Waind, J. Inorg. Nucl. Chem., 23, 207 (1961);
88. R. J. Fitzgerald, B. B. Hutchinson, and K. Nakamoto, Inorg. Chem., 9, 2618 (1970);
89. N. Tanaka and Y. Sato, Bull. Chem. Soc. Jap., 81, 2059 (1968), and references therein.
90. W. M. Reiff, results to be published.