Heterocyclic organotellurium compounds as precursors for new organometallic derivatives of rhodium

Abstract

The reaction of the pentamethylcyclopentadienylrhodium(III) dichloride dimer, [{Rh(η-C₅Me₅)Cl₂}₂ ], with tellurophene in the presence of Ag(O₃SCF₃) afforded the expected [Rh(η-C₅Me₅)(η⁵-C₄ H₄Te)][O₃SCF₃]₂1 which on reaction with [Co(cp)₂] (cp = η-C₅H₅) gives a rhodacyclic material [Rh(η-C₅Me₅){η⁵-C₅ H₄Rh(η-C₅Me₅)}] 2. The reaction of 2 with [Fe₃(CO)₁₂] gave [Rh(η-C₅Me₅){η⁵-C₄ H₄Fe(CO)₃}] 3. The reaction of [{Rh(η-C₅Me₅)Cl₂}₂ ] with dibenzotellurophene, dbt, in the presence of Ag(O₃SCF₃) gives [Rh(η-C₅Me₅)(dbt)][O₃SCF₃ ]₂4, in which the mode of coordination of dbt in CDCl₃ solution appears to be η¹. The reaction of 4 with [Co(cp)₂] and [Fe₃(CO)₁₂] gave a variety of products including [Rh(η-C₅Me₅)(C₁₂H₈)( η¹-dbt)] 5, a known dibenzoferrole, 6, and compound 7 in which the η¹-dbt of 5 is substituted by CO. Also isolated were the known [{Fe(η-C₅Me₅)(CO)₂} ₂] 8 and FeTe. The direct reaction of [{Rh(η-C₅Me₅)Cl₂}₂ ] and dbt gave [Rh(η-C₅Me₅)Cl₂(η¹ -dbt)]. Two complexes of 2-telluraindane were synthesized for comparison, [Rh(η-C₅Me₅)(C₈H₈ Te)][O₃SCF₃]₂10 and [Rh(η-C₅Me₅)Cl₂(C₈H ₈Te)] 11 the latter showing fluxionality about co-ordinated tellurium at room temperature. It is suggested that the magnitude of J (¹²⁵Te–¹⁰³Rh) has the potential to differentiate the modes of co-ordination of heterocyclic tellurium compounds to rhodium. The crystal and molecular structures have been determined for compounds 5, 7 and 9.

References

1. K. Singh, W. R. McWhinnie, H. L. Chen, M. Sun and T. A. Hamor, J. Chem. Soc., Dalton Trans., 1996, 1545.
2. T. B. Rauchfuss, Prog. Inorg. Chem., 1991, 39, 259.
3. R. J. Angelici, Acc. Chem. Res., 1988, 21, 387, J. Coord. Chem. Rev., 1990, 105, 61.
4. S. Luo, A. E. Ogilvy, T. B. Rauchfuss, A. L. Rheingold and S. R. Wilson, Organometallics, 1991, 10, 1002.
5. S. Luo, A. E. Skaugset, T. B. Rauchfuss and S. R. Wilson, J. Am. Chem. Soc., 1992, 114, 1732.
6. M. G. Choi and R. J. Angelici, J. Am. Chem. Soc., 1989, 111, 8753.
7. E. O. Fischer and K. Öfele, Chem. Ber., 1958, 91, 2395.
8. X. Ma, K. Sakanishi, T. Isoda and I. Mochida, Energy Fuels, 1995, 9, 33.
9. K. M. Rao, C. L. Day, R. A. Jocobsen and R. J. Angelici, Inorg. Chem., 1991, 30, 5046.
10. E. O. Fischer, H. A. Goodwind, C. G. Kreiter, H. D. Simmons, K. Sonogashira and S. B. Wild, J. Organomet. Chem., 1980, 180, 265.
11. J. Wang, K. Moseley and P. M. Maitlis, J. Am. Chem. Soc., 1969, 91, 5046.
12. W. Lohner and K. Praefcke, Chem. Ber., 1978, 111, 3745.
13. J. D. McCullough, Inorg. Chem., 1975, 14, 2285.
14. P. Granger, S. Chepelle, W. R. McWhinnie and A. Z. Al-Rubaie, J. Organomet. Chem., 1981, 220, 149.
15. R. G. Teller and J. Williams, Inorg. Chem., 1980, 19, 2770.
16. A. Z. Al-Rubaie, W. R. McWhinnie, P. Granger and S. Chapelle, J. Organomet. Chem., 1982, 234, 287.
17. TEXSAN, Single Crystal Structure Analysis Software, version 1.6, Molecular Structure Corporation, Houston, TX, 1993.
18. G. M. Sheldrick, SHELXL 93, Program for Crystal Structure Refinement, University of Göttingen, 1993.
19. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
20. J. Chen, L. M. Daniels and R. J. Angelici, J. Am. Chem. Soc., 1990, 112, 199.
21. C. J. White, T. Wang, R. A. Jacobsen and R. J. Angelici, Organometallics, 1994, 13, 4474.
22. Cambridge Structural Database System, release. Cambridge Crystallographic Data Centre, April 1996.
23. S. Schulz, M. Andruh, T. Pape, T. Heinze, H. W. Roesky, L. Haming, A. Kuhn and R. Herbst-Irmer, Organometallics, 1994, 13, 4004.
24. M. Di Vaira, M. Peruzzini and P. Stoppioni, Inorg. Chem., 1989, 28, 4614.
25. M. Di Vaira, M. Peruzzini and P. Stoppioni, Inorg. Chem., 1991, 30, 1001.
26. C. Perthuisot and W. D. Jones, J. Am. Chem. Soc., 1994, 116, 3647.
27. J. D. McCullough, Inorg. Chem., 1975, 14, 2639.
28. F. H. Allen, D. G. Watson, L. Brammer, A. G. Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.