Molecular orbital analysis of the metal–hydrazide(2–) bonding in co-ordination chemistry †

Abstract

The bonding in mono- and bis-hydrazido metal complexes has been studied with the help of EHMO and ab initio calculations on various models as well as on free hydrazide. The theoretical results have been analysed together with a collection of structural data obtained through a Cambridge Data Base search covering 118 compounds. Although generally described as being a hydrazide(2–) ligand, its oxidation state is often closer –1 in early transition-metal complexes, corresponding to the following occupation of its frontier orbitals: (σ_n)²(π_NN)²(π_σ)²(π*_NN)¹. The occupied hydrazido π_NN orbital, which does not interact significantly with the metal, is largely responsible for the significant double-bond character of the N–N bond. The partial population of the π*_NN level, which tends to reduce the N–N bond order, is partly balanced by depopulation of the somewhat antibonding π_σ orbital. Assuming the traditional hydrazido(2–) formal charge, the ligand is a six-electron donor in monohydrazido metal species if co-ordinated linearly. If significantly bent, it is a four-electron donor. In the case of cis bis(hydrazido) species, the two formally hydrazide(2–) ligands act generally as a 10-electron donor system.

References

1. (a) W. A. Nugent and J. M. Mayer, Metal–Ligand Multiple Bonds, Wiley-Interscience, New York, 1988; (b) W. A. Nugent and B. L. Haymore, Coord. Chem. Rev., 1980, 31, 123; (c) J. A. McCleverty, Transition Met. Chem., 1987, 12, 283; (d) R. A. Henderson, G. J. Leigh and C. J. Pickett, Adv. Inorg. Chem. Radiochem., 1983, 27, 197; (e) B. F. G. Johnson, B. L. Haymore and J. R. Dilworth, in Comprehensive Coordination Chemistry, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon, Oxford, 1987, vol. 2, p. 99; (f) D. Sutton, Chem. Rev., 1993, 93, 995; (g) M. Hirsch-Kuchma, T. Nicholson, A. Davison and A. G. Jones, J. Chem. Soc., Dalton Trans., 1997, 3189; (h) M. H. Chisholm and I. P. Rothwell, in Comprehensive Coordination Chemistry, eds. G. Wilkinson, R. D. Gillard and J. A. McCleverty, Pergamon, Oxford, 1987, vol. 2, p. 161; (i) K. Dehnicke and J. Strähle, Polyhedron, 1989, 8, 707; (j) K. Dehnicke and J. Strähle, Chem. Rev., 1993, 93, 981; (k) D. E. Wigley, Prog. Inorg. Chem., 1994, 42, 239.
2. G. A. Heath, R. Mason and K. M. J. Thomas, J. Am. Chem. Soc., 1974, 96, 259.
3. R. Mason, K. M. J. Thomas, J. A. Zubieta, P. G. Douglas, A. R. Galbraith and B. L. J. Shaw, J. Am. Chem. Soc., 1974, 96, 260.
4. F. C. March, R. Mason and K. M. J. Thomas, J. Organomet. Chem., 1975, 96, C43.
5. M. Veith, Angew. Chem., Int. Ed. Engl., 1976, 15, 387.
6. M. Hidai, T. Kodama, M. Sato, M. Harakawa and Y. Uchida, Inorg. Chem., 1976, 15, 2694.
7. V. Day, T. A. George, S. D. A. Iske and S. D. Wagner, J. Organomet. Chem., 1976, 112, C55.
8. C. Redshaw, V. C. Gibson, W. Clegg, A. J. Edwards and B. Miles, J. Chem. Soc., Dalton Trans., 1979, 3343.
9. J. Chatt, M. E. Fakley, R. L. Richards, I. R. Hanson and D. L. Hughes, J. Organomet. Chem., 1979, 170, C6.
10. M. W. Bishop, J. Chatt, J. R. Dilworth, M. B. Hursthouse and M. Motevalli, J. Chem. Soc., Dalton Trans., 1979, 1600.
11. J. Chatt, J. R. Dilworth, P. L. Dahlstrom and J. Zubieta, J. Chem. Soc., Chem. Commun., 1980, 786.
12. D. L. Hughes, Acta Crystallogr., Sect. B, 1981, 37, 557.
13. I. R. Hanson and D. L. Hughes, J. Chem. Soc., Dalton Trans., 1981, 390.
14. K. Iwanami, Y. Mizobe, T. Takahashi, T. Kodama, Y. Uchida and M. Hidai, Bull. Chem. Soc. Jpn., 1981, 54, 1773.
15. R. J. Burt, J. R. Dilworth, G. J. Leigh and J. Zubieta, J. Chem. Soc., Dalton Trans., 1982, 2295.
16. J. Chatt, M. E. Fakley, P. B. Hitchcock, R. L. Richards and N. T. Luong-Thi, J. Chem. Soc., Dalton Trans., 1982, 345.
17. P. L. Dahlstrom, J. R. Dilworth, P. Schulman and J. Zubieta, Inorg. Chem., 1982, 21, 933.
18. J. Chatt, B. A. L. Crichton, J. R. Dilworth, P. Dahlstrom and J. A. Zubieta, J. Chem. Soc., Dalton Trans., 1982, 1041.
19. H. Nishihara, T. Mori, Y. Tsurita, K. Nakano, T. Saito and T. Sasaki, J. Am. Chem. Soc., 1982, 104, 4367.
20. C. F. Barrientos-Penna, F. W. B. Einstein, T. Jones and D. Sutton, Inorg. Chem., 1982, 21, 2578.
21. F. W. B. Einstein, T. Jones, A. J. L. Hanlan and D. Sutton, Inorg. Chem., 1982, 21, 2585.
22. J. R. Dilworth, J. Hutchinson, L. Throop and J. Zubieta, Inorg. Chim. Acta, 1983, 79, 208.
23. K. Komori, T. Kodama, D.-M. Jin, T. Takahashi, Y. Uchida and M. Hidai, Chem. Lett., 1983, 465.
24. M. Hidai, K. Komori, T. Kodama, D.-M. Jin, T. Takahashi, S. Sugiura, Y. Uchida and Y. Mizobe, J. Organomet. Chem., 1984, 272, 155.
25. J.-P. Mahy, P. Battioni, D. Mansuy, J. Fisher, R. Weiss, J. Mispelter, I. Morgenstern-Badarau and P. Gans, J. Am. Chem. Soc., 1984, 106, 1699.
26. T. Nicholson and J. Zubieta, J. Chem. Soc., Chem. Commun., 1985, 367.
27. J. R. Dilworth, S. A. Harrison, D. R. M. Walton and E. Schweda, Inorg. Chem., 1985, 24, 2594.
28. P. J. Blower, J. R. Dilworth, G. J. Leigh, B. D. Neaves, F. B. Normanton, J. Hutchinson and J. A. Zubieta, J. Chem. Soc., Dalton Trans., 1985, 2647.
29. K. Gebreyes, J. Zubieta, T. A. George, L. M. Koczon and R. C. Tisdale, Inorg. Chem., 1986, 25, 405.
30. M. Hidai, S. Aramaki, K. Yoshida, T. Kodama, T. Takahashi, Y. Uchida and Y. Mizobe, J. Am. Chem. Soc., 1986, 108, 1562.
31. S. N. Shaikh and J. Zubieta, Inorg. Chim. Acta, 1986, 115, L19.
32. J. Bultitude, L. F. Larkworthy, D. C. Povey, G. W. Smith, J. R. Dilworth and G. J. Leigh, J. Chem. Soc., Chem. Commun., 1986, 1748.
33. T. Nicholson, P. Lombardi and J. Zubieta, Polyhedron, 1987, 6, 1577.
34. T. Nicholson and J. Zubieta, Polyhedron, 1988, 7, 171.
35. S. N. Shaikh and J. Zubieta, Inorg. Chem., 1988, 27, 1896.
36. M. A. Bakar, D. L. Hughes, W. Hussain, G. J. Leigh, C. J. Macdonald and H. M. Ali, J. Chem. Soc., Dalton Trans., 1988, 2545.
37. M. A. Bakar, D. L. Hughes and G. J. Leigh, J. Chem. Soc., Dalton Trans., 1988, 2525.
38. H. Kang and J. Zubieta, J. Chem. Soc., Chem. Commun., 1988, 1192.
39. T.-C. Hsieh, T. Nicholson and J. Zubieta, Inorg. Chem., 1988, 27, 241.
40. S. N. Shaikh and J. Zubieta, Inorg. Chim. Acta, 1988, 144, 147.
41. T. A. George, L. M. Koczon, R. C. Tisdale, K. Gebreyes, L. Ma, S. N. Shaikh and J. Zubieta, Polyhedron, 1990, 9, 545.
42. H. Oshita, Y. Mizobe and M. Hidai, Chem. Lett., 1990, 1303.
43. M. D. FitzRoy, G. D. Fallon, K. M. Murray, J. M. Frederiksen and E. R. T. Tiekink, Inorg. Chim. Acta, 1990, 169, 79.
44. J. E. Barclay, A. Hills, D. L. Hughes, G. J. Leigh, C. J. Macdonald, M. A. Bakar and M. H. Ali, J. Chem. Soc., Dalton Trans., 1990, 2503.
45. J. Zubieta, E. Block, G. Ofori-Okai and K. Tang, Inorg. Chem., 1990, 29, 4595.
46. A. C. Street, Y. Mizobe, F. Gotoh, I. Mega, H. Oshita and M. Hidai, Chem. Lett., 1991, 383.
47. C. Bustos, C. Manzur, H. Gonzalez, R. Schrebler, D. Carrillo, C. Bois, Y. Jeannin and P. Gouzerh, Inorg. Chim. Acta, 1991, 185, 25.
48. E. Block, H. Kang and J. Zubieta, Inorg. Chim. Acta, 1991, 181, 227.
49. E. Block, M. Gernon, H. Kang, G. Ofori-Okai and J. Zubieta, Inorg. Chem., 1991, 30, 1736.
50. D. Carrillo, F. Robert and P. Gouzerh, Inorg. Chim. Acta, 1992, 197, 209.
51. B. A. Arndtsen, T. K. Schoch and L. McElwee-White, J. Am. Chem. Soc., 1992, 114, 7041.
52. T. Aoshima, Y. Mizobe, M. Hidai and J. Tsuchiya, J. Organomet. Chem., 1992, 423, 39.
53. H. Oshita, Y. Mizobe and M. Hidai, Organometallics, 1992, 11, 4116.
54. J. R. Dilworth, P. Jobanputra, S. J. Parrott, R. M. Thompson, D. C. Povey and J. A. Zubieta, Polyhedron, 1992, 11, 147.
55. J. R. D. DeBord, T. A. George, Y. Chang, K. Chen and J. Zubieta, Inorg. Chem., 1993, 32, 785.
56. T. A. George, B. B. Kaul, K. Chen and J. Zubieta, Inorg. Chem., 1993, 32, 1706.
57. J. R. Dilworth, P. Jobanputra, J. R. Miller, S. J. Parrott, Q. Chen and J. Zubieta, Polyhedron, 1993, 12, 513.
58. G. M. Coia, P. S. White, T. J. Meyer, D. A. Wink, L. K. Keefer and W. M. Davis, J. Am. Chem. Soc., 1994, 116, 3649.
59. M. Jimenez-Tenorio, M. C. Puerta, P. Valerga and D. L. Hughes, J. Chem. Soc., Dalton Trans., 1994, 2431.
60. H. Seino, Y. Ishii and M. Hidai, J. Am. Chem. Soc., 1994, 116, 7433.
61. A. C. Stergiou, S. Bladenopoulou and C. Tsiamis, Inorg. Chim. Acta, 1994, 217, 61.
62. C. Bustos, C. Manzur, D. Carrillo, F. Robert and P. Gouzerh, Inorg. Chem., 1994, 33, 1427.
63. M. Retboll, E. R. Möller, R. G. Hazell and K. A. Jörgensen, Acta Chem. Scand., 1995, 49, 278.
64. J. Li-Kao, O. Gonzalez, R. Mariezcurreña, R. Baggio, M. T. Garland and D. Carrillo, Acta Crystallogr., Sect. C, 1995, 51, 2486.
65. H. Seino, Y. Ishii, T. Sasagawa and M. Hidai, J. Am. Chem. Soc., 1995, 117, 12 181.
66. M. B. Gernet, H. Kooijman, W. P. Hiller, J. R. Dilworth and S. J. Parrott, Acta Crystallogr., Sect. C, 1996, 52, 545.
67. H. Seino, Y. Ishii and M. Hidai, Inorg. Chem., 1997, 36, 161.
68. C. Manzur, C. Bustos, D. Carrillo, D. Boys and J.-R. Hamon, Inorg. Chim. Acta, 1997, 255, 73.
69. J. R. Dilworth, V. C. Gibson, C. Z. Lu, J. R. Miller, C. Redshaw and Y. F. Zheng, J. Chem. Soc., Dalton Trans., 1997, 269.
70. M. L. H. Green, J. T. James, J. F. Saunders and J. Souter, J. Chem. Soc., Dalton Trans., 1997, 1281.
71. J. T. Barry, M. H. Chisholm, K. Folting, J. C. Huffman and W. E. Streib, Polyhedron, 1997, 16, 2113.
72. V. Körner, G. Huttner, S. Vogel, A. Barth and L. Zsolnai, Chem. Ber. Recl., 1997, 130, 489.
73. G. M. Coia, M. Devenney, P. S. White, T. J. Meyer and D. A. Wink, Inorg. Chem., 1997, 36, 2341.
74. M. L. H. Green, J. T. James and A. N. Chernega, J. Chem. Soc., Dalton Trans., 1997, 1719.
75. J. Chatt, B. A. L. Crichton, J. R. Dilworth, P. L. Dahlstrom, R. Gutkoska and J. A. Zubieta, Transition Met. Chem., 1979, 4, 271.
76. B. A. L. Crichton, J. R. Dilworth, P. L. Dahlstrom and J. Zubieta, Transition Met. Chem, 1980, 5, 316.
77. J. R. Dilworth and J. Zubieta, J. Chem. Soc., Chem. Commun., 1981, 132.
78. J. R. Dilworth, J. Zubieta and J. R. Hyde, J. Am. Chem. Soc., 1982, 104, 365.
79. J. Chatt, B. A. L. Crichton, J. R. Dilworth, P. Dahlstrom, R. Gutkoska and J. Zubieta, Inorg. Chem., 1982, 21, 2383.
80. J. R. Dilworth, R. L. Richards, P. Dahlstrom, J. Hutchinson, S. Kumar and J. Zubieta, J. Chem. Soc., Dalton Trans., 1983, 1489.
81. P. T. Bishop, J. R. Dilworth, S. Morton and J. A. Zubieta, J. Organomet. Chem., 1988, 341, 373.
82. A. A. Danopoulos, G. Wilkinson and D. J. J. Williams, J. Chem. Soc., Dalton Trans., 1994, 907.
83. C. Bustos, C. Manzur, D. Carrillo, F. Robert and P. Gouzerh, Inorg. Chem., 1994, 33, 4937.
84. P. B. Kettler, Y.-D. Chang and J. Zubieta, Inorg. Chem., 1994, 33, 5864.
85. C. Manzur, C. Bustos, D. Carrillo, F. Robert and P. Gouzerh, Inorg. Chim. Acta, 1996, 249, 245.
86. C. Manzur, D. Carrillo, F. Robert, P. Gouzerh, P. Hamon and J.-R. Hamon, Inorg. Chim. Acta, 1998, 268, 199.
87. C. Manzur, D. Carrillo and D. Boys, Acta Crystallogr., Sect. C, 1997, 53, 1401.
88. C. Manzur, D. Carrillo, F. Robert, P. Gouzerh and J.-R. Hamon, unpublished work.
89. A. A. Danopoulos, R. S. Hay-Motherwell, G. Wilkinson, T. K. N. Sweet and M. B. Hursthouse, Polyhedron, 1997, 16, 1081.
90. C. Manzur, D. Carrillo, R. Baggio and M. T. Garland, J. Chem. Crystallogr., 1997, 27, 339.
91. Cambridge Data Base System, version 5.13, Cambridge Crystallographic Data Centre, 1997.
92. J. Emsley, The Elements, Clarendon Press, Oxford, 1989.
93. D. L. Dubois and R. Hoffmann, Nouv. J. Chim., 1977, 1, 479.
94. M. L. H. Green, G. Hogarth, P. C. Konidaris and P. Mounfort, J. Chem. Soc., Dalton Trans., 1991, 3781; M. H. Schofield, T. P. Kee, J. T. Anhaus, R. R. Schrock, K. H. Johnson and W. M. Davies, Inorg. Chem., 1990, 30, 3595; B. A. Arndtsen, H. F. Sleiman, A. K. Chang and L. McElvee-White, J. Am. Chem. Soc., 1991, 113, 4971; D. H. Williams, J. P. Mitchell, A. D. Poole, U. Siemeling, W. Clegg, D. C. R. Hockless, P. A. O'Neil and V. C. Gibson, J. Chem. Soc., Dalton Trans., 1992, 739; T. R. Cundari, J. Am. Chem. Soc., 1992, 114, 7879; D. S. Williams, M. H. Schofield and R. R. Schrock, Organometallics, 1993, 12, 4560; T. R. Cundari, Organometallics, 1993, 12, 4971; P. D. Lyne and D. M. P. Mingos, J. Organomet. Chem., 1994, 478, 141; A. K. Burrell, D. L. Clark, P. L. Gordon, A. P. Sattelberger and J. C. Bryan, J. Am. Chem. Soc., 1994, 116, 3813; P. Mountford and D. Swallow, J. Chem. Soc., Chem. Commun., 1995, 2357; M. T. Benson, J. C. Bryan, A. K. Burrell and T. R. Cundari, Inorg. Chem., 1995, 34, 2348.
95. J. H. Osborne, A. L. Rheingold and W. C. Trogler, J. Am. Chem. Soc., 1985, 107, 7945; K. A. Jørgensen, Inorg. Chem., 1993, 32, 1521; J. C. Green, M. L. H. Green, J. T. James, P. C. Konidaris, G. H. Maunder and P. Mountford, J. Chem. Soc., Chem. Commun., 1992, 1361.
96. N. M. Kostic and R. F. Fenske, J. Am. Chem. Soc., 1981, 103, 4677.
97. R. E. Cramer, F. Edelmann, A. L. Mori, S. Roth, J. W. Gilje, K. Tatsumi and A. Nakamura, Organometallics, 1988, 7, 841.
98. A. K. Rappé, Inorg. Chem., 1984, 23, 995.
99. Z. Lin and M. B. Hall, Coord. Chem. Rev., 1993, 123, 149.
100. (a) R. J. Deeth, J. Chem. Soc., Dalton Trans., 1991, 1875; (b) A. K. Rappé and W. A. Goddard III, J. Am. Chem. Soc., 1982, 104, 448; (c) A. K. Rappé and W. A. Goddard III, J. Am. Chem. Soc., 1982, 104, 3287; (d) N. D. Silavwe, M. R. M. Bruce, C. E. Philbin and D. R. Tyler, Inorg. Chem., 1988, 27, 4669; (e) G. Peng, J. Nichols, E. A. McCullough, jun. and J. T. Spence, Inorg. Chem., 1994, 33, 2864; (f) A. J. Bridgeman, L. Davis, S. J. Dixon, J. C. Green and I. N. Wright, J. Chem. Soc., Dalton Trans., 1995, 1023; (g) M. A. Pietsch and M. B. Hall, Inorg. Chem., 1996, 35, 1273.
101. R. Hoffmann, J. Chem. Phys., 1963, 39, 1397; R. Hoffman and W. N. Lipscomb, J. Chem. Phys., 1962, 36, 2179.
102. J. H. Ammeter, H.-B. Bürgi, J. C. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686.
103. C. Mealli and D. M. Proserpio, J. Chem. Educ., 1990, 67, 399.
104. GAUSSIAN 94, revision B.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheesman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al Laham, V. G. Zakrzewsky, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales and J. A. Pople, Gaussian Inc., Pittsburgh, PA, 1995.
105. G. A. Patersson, A. Bennett, T. G. Tensfeldt, M. A. El-Laham, W. A. Shirley and J. Mantzaris, J. Chem. Phys., 1988, 89, 2193.
106. C. Møller and M. S. Plesset, Phys. Rev., 1934, 46, 618.
107. W. A. Latham, L. A. Curtiss, W. J. Hehre, J. B. Lisle and J. A. Pople, Prog. Phys. Org. Chem., 1974, 11, 175.
108. J. R. Dilworth, A. Garcia-Rodriguez, G. J. Leigh and J. N. Murrell, J. Chem. Soc., Dalton Trans., 1983, 455.
109. R. Hoffmann, Angew. Chem., Int. Ed. Engl., 1982, 21, 711.
110. T. A. Albright, J. K. Burdett and M.-H. Whangbo, Orbital Interctions in Chemistry, Wiley, New York, 1985.
111. S. Cai, D. Hoffman and D. A. Wierda, Organometallics, 1996, 15, 1023.