A survey of terminal chalcogenido complexes of the transition metals : Trends in their distribution and the variation of their M=E bond lengths

Polyhedron

Volumn 16, Issue 7, 1997, Pages 1031-1045

  Trnka, Tina M ^a   Parkin, Gerard ^a  

^a Columbia University ^*  (United States)

Author keywords

Chalcogen; Metal; Oxo; Selenido; Sulfido; Tellurido

Indexed keywords

EID: 0001464902     PISSN: 02775387     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0277-5387(96)00411-1     Document Type: Article

References (75)

1. Nugent, W. A. and Mayer, J. M., Metal-Ligand Multiple Bonds. Wiley-Interscience, New York. 1988.
2. There is some controversy as to whether or not oxygen should be considered a chalcogen. The term chalcogen appears to have developed directly from the words "chalkosphäre" and "chalkophile", coined in the earlier part of this century by Goldschmidt, a geochemist [2a,b]. Goldschmidt used "chalkosphäre" to describe a region of the earth that is rich in metal oxides and sulfides, i.e. ores, while "chalkophile" was used to describe elements found in this region (e.g. Fe, Cu, Zn). Since these names derived from the Greek word "chalkos" (χαλκoσ) meaning copper, a literal translation of chalcogen is "copper-former". However, Jensen has rationalized that since "chalkos" may also be interpreted as copper alloy or ore, and since copper is not the only element considered to be a "chalkophile", a more pertinent interpretation of the term chalcogen is "ore-former" [2c]. Consequently, oxygen is appropriately considered to be a chalcogen, a term that has, in fact, been approved by IUPAC as the collective name for the group 16 elements : O, S, Se, Te, Po [2d]. (a) Goldschmidt, V. M., J. Chem. Soc. (London), 1937, 655 ;
3. (b) Goldschmidt, V. M., Die Naturwissenschaften, 1930, 18, 999 ;
4. (c) Jensen, K. A., Chemistry and Industry, 1964, 49, 2016 ;
5. (d) IUPAC Nomenclature of Inorganic Chemistry, Recommendations 1990, ed. G. J. Leigh. Blackwell, London, 1990.
6. -, however, have been generated in the gas phase [3b]. (a) Bonanno, J. B., Wolczanski, P. T. and Lobkovsky, E. B., J. Am. Chem. Soc. 1994, 116, 11159 ;
7. (b) Arnold, F. P. Jr, Ridge, D. P. and Rheingold, A. L., J. Am. Chem. Soc. 1995, 117, 4427.
8. Mayer, J. M., Inorg. Chem. 1988, 27, 3899.
9. For example, rather than forming terminal chalcogenido complexes, the heavier chalcogens are commonly found either (i) to bridge two or more metal centers [5a-e] or (ii) to form polychalcogenide ligands [5f-q]. (a) Herrmann, W. A., Angew. Chem., Int. Ed. Engl. 1986, 25, 56 ;
10. (b) Compton, N. A., Errington, R. J. and Norman, N. C., Adv. Organomet. Chem. 1990, 31, 91 ;
11. (c) Housecraft, C. E., in Inorganometallic Chemistry, ed. T. P. Fehlner. Plenum Press, New York, 1992, Ch 3, pp. 73-178 ;
12. (d) Fenske, D., Ohmer, J., Hachgenei, J. and Merzweiler, K., Angew. Chem., Int. Ed. Engl. 1988, 27, 1277 ;
13. (e) Dance, I. and Fisher, K., Prog. Inorg. Chem. 1994, 41, 637 ;
14. (f) Müller, A. and Diemann, E., Adv. Inorg. Chem. 1987, 31, 89 ;
15. (g) Draganjac, M. and Rauchfuss, T. B., Angew. Chem., Int. Ed. Eng. 1985, 24, 742 ;
16. (h) Wachter, J., Angew. Chem., Int. Ed. Engl. 1989, 28, 1613 ;
17. (i) Beck, J., Angew. Chem., Int. Ed. Engl. 1994, 33, 163 ;
18. (j) Böttcher, P., Angew. Chem.' Int. Ed. Engl. 1988, 27, 759 ;
19. (k) Kanatzidis, M. G., Comm. Inorg. Chem. 1990, 10, 161 ;
20. (m) Kolis, J. W., Coord. Chem. Rev. 1990, 105, 195 ;
21. (n) Roof, L. C. and Kolis, J. W., Chem. Rev. 1993, 93, 1037 ;
22. (o) Ansari, M. A. and Ibers, J. A., Coord. Chem. Rev. 1990, 100, 223 ;
23. (p) Kanatzidis, M. G. and Huang, S.-P., Coord. Chem. Rev. 1994, 130, 509 ;
24. (q) Ansari, M. A., McConnachie, J. M. and Ibers, J. A., Acc. Chem. Res. 1993, 26, 574.
25. Howard, W. A., Waters, M. and Parkin, G., J. Am. Chem. Soc. 1993, 115, 4917 ;
26. Howard, W. A., Trnka, T. M., Waters, M. and Parkin, G., J. Organomet. Chem., in press.
27. For a recent review describing the distribution of structurally-characterized alkoxide, thiolate, selenolate and tellurolate complexes, see : Arnold, J., Prog. Inorg. Chem. 1995, 43, 353.
28. Rice, D. A., Coord. Chem. Rev. 1978, 227, 199 ;
29. Vahrenkamp, H., Agnew. Chem., Int. Ed. Engl. 1975, 14, 322 ;
30. Müller, A., Diemann, E., Jostes, R. and Bögge, H., Angew. Chem., Int. Ed. Engl. 1981, 20, 934 ;
31. Müller, A. and Diemann, E., in Comprehensive Coordination Chemistrv, Vol. 2, ed. G. Wilkinson, R. D. Gillard and J. A. McCleverty. Pergamon Press, Oxford, 1987, Ch. 16.1, pp. 515-550 ;
32. Müller, A., Polyhedron, 1986, 5, 323-340.
33. Berry, F. J., in Comprehensive Coordination Chemistry, Vol. 2, ed. G. Wilkinson, R. D. Gillard and J. A. McCleverty. Pergamon Press : Oxford, 1987, Ch. 17, pp. 661-674.
34. For some leading articles on multiple bonding of the heavier main group elements, see : Kutzelnigg, W., Angew. Chem., Int. Ed. Engl. 1984, 23, 272 ;
35. Gusel'nikov, L. E. and Nametkin, N. S., Chem. Rev. 1979, 79, 529 ;
36. Jutzi, P., Angew Chem., Int. Ed. Engl. 1975, 14, 232 ;
37. Norman, N. C., Polyhedron 1993, 12, 2431 ;
38. Schmidt, M. W., Truong, P. N. and Gordon, M. S., J. Am. Chem. Soc. 1987, 109, 5217 ;
39. Jacobsen, H. and Ziegler, T., J. Am. Chem. Soc. 1994, 116, 3667 ;
40. Huheey, J. E., Keiter, E. A. and Keiter, R. L., Inorganic Chemistry: Principles of Structure and Reactivity, 4th Edn. Harper Collins, New York, 1993, Ch. 18, pp. 861-875 ;
41. Jacobsen, H. and Ziegler, T., Comm. Inorg. Chem. 1995, 17, 301.
42. Hay-Motherwell, R. S., Wilkinson, G., Hussain-Bates, B. and Hursthouse, M. B., Polyhedron, 1993, 12, 2009.
43. Mayer, J. M., Comm. Inorg. Chem. 1988, 8, 125.
44. For a recent review describing the electronic structures of metal-oxo complexes, see : Miskowski, V. M., Gray, H. B. and Hopkins, M. D., Adv. Trans. Met. Comp. 1996, 1, 159.
45. For further discussion of the influence of filled-filled repulsions in transition metal chemistry, see : Caulton, K. G., New. J. Chem. 1994, 18, 25.
46. Parkin, G. and Bercaw, J. E., J. Am. Chem. Soc. 1989, 111, 391 ;
47. Parkin G. and Bercaw, J. E., Polyhedron, 1988, 7, 2053.
48. A crude estimate of the relative number of studies on elements of the second and third transition series may be obtained by examining the number of papers that cite these elements themselves either in the title or abstract. For example, using the names of the elements as keywords, there are ca 25% more listings in the Science Citation Index (1982-1996) for the elements of the second transition series than for the third transition series.
49. +] bonds. For simplicity, however, in this paper we use the representation [M=E] to refer generally to any terminal chalcogenido moiety, regardless of bond order.
50. Wood, P. T., Pennington, W. T., Kolis, J. W., Wu, B. and O'Connor, C. J., Inorg. Chem. 1993, 32, 129.
51. The mean W-S single bond length (2.390 Å, with a range of 2.107-2.721 å) is that for complexes in which sulfur is two-coordinate.
52. Lorenz, I.-P., Walter, G. and Hiller, W., Chem. Ber. 1990, 123, 979.
53. Murphy, V. J. and Parkin, G., J. Am. Chem. Soc. 1995, 117, 3522.
54. Some related problems in ligand assignment have been noted with the reformulation of complexes originally proposed to be alkoxides as, in fact, alcohol derivatives. See : Koch, S. A. and Lincoln, S., Inorg. Chem., 1982, 21, 2904.
55. 3 [1.803(11) Å] is considerably longer than the mean value (1.678 Å) reported by Mayer for mono-oxo molybdenum complexes.
56. Chatt, J., Manojlovic-Muir, L. and Muir, K. W., J. Chem. Soc., Chem. Commun. 1971, 655 ;
57. Manojlovic-Muir, L., J. Chem. Soc. (A) 1971, 2796 ;
58. Manojlovic-Muir, L. and Muir, K. W., J. Chem. Soc., Dalton Trans. 1972, 686 ;
59. Haymore, B. L., Goddard, III, W. A. and Allison, J. N., Proc. Int. Conf. Coord. Chem., 23rd 1984, 535.
60. Jean, Y., Lledos, A., Burdett, J. K. and Hoffmann, R., J. Am. Chem. Soc. 1988, 110, 4506 ;
61. Jean, Y., Lledos, A., Burdett, J. K. and Hoffmann, R., J. Chem. Soc., Chem. Commun. 1988, 140.
62. Parkin, G., Acc. Chem. Res. 1992, 25, 455 ;
63. Parkin, G., Chem. Rev. 1993, 93, 887.
64. Mayer has noted, however, that M=O bond lengths do increase slightly in the presence of a second multiply bonded ligand (e.g. oxo, nitrido, imido).
65. Rabinovich, D. and Parkin, G., Inorg. Chem 1996, 34, 6341.
66. L is a two-electron donor and X is a one-electron donor ligand. See: Green, M. L. H., J. Organomet. Chem. 1995, 500, 127.
67. Howard, W. and Parkin, G., J. Am. Chem. Soc. 1994, 116, 606.
68. See, for example the empirical Schomaker Stevenson equation, d(A - B) = r(A) + r(B) - c|χ(A) - χ(B)|. Schomaker, V. and Stevenson, D. P., J. Am. Chem. Soc. 1941, 63, 37 ;
69. Wells, A. F., J. Chem. Soc. 1949, 55 ;
70. Wells, A. F., Structural Inorganic Chemistry, 5th edn, Oxford University Press, London. 1984, pp. 287-291.
71. Benson, M. T., Cundari, T. R., Lim, S. J., Nguyen, H. D. and Pierce-Beaver, K., J. Am. Chem. Soc. 1994, 116, 3955 ;
72. Benson, M. T., Cundari, T. R., Li, Y. and Strohecker, L. A., Int. J. Quantum Chem. : Quantum Chemistry Symposium 1994, 28, 181 ;
73. Gordon, M. S. and Cundari, T. R., Coord. Chem. Rev. 1996, 147, 87.
74. The metallic radii of the transition elements are effectively identical to the covalent radii derived by consideration of the bond lengths (Å) in diatomic MH molecules: Ti (1.324), V (1.224), Cr (1.176), Mn (1.171), Fe (1.165), Co (1.162), Zr (1.454), Nb (1.342), Mo (1.296), Tc (1.271), Ru (1.246), Rh (1.252), Hf (1.442), Ta (1.343), W (1.304), Re (1.283), Os (1.260), Ir (1.265). Data taken from Pauling, L. The Nature of the Chemical Bond, 3rd edn. Cornell University Press, Ithaca, 1960, p. 256.
75. Page, E. M., Rice, D. A., Hagen, K., Hedberg, L. and Hedberg, K., Inorg. Chem. 1991, 30, 4758.