Syntheses and characterisation of rhenium-(III) and -(V) complexes containing aminophosphine ligands. Crystal structures of [Re^VOCl₂(OMe)L] and [Re^IIICl₃L(PPh₃)], L = o-(diphenylphosphino)-N ,N′-dimethylaniline

Abstract

Substitution reactions of labile rhenium(V) precursors with o-(diphenylphosphino)-N,N′ -dimethylaniline, L, gave a series of monooxorhenium(V) complexes of general formula [ReOX₂Y(L)] (X = Y = Cl 1; X = Cl, Y = OMe 2) and [ReOX₂(OEt)L] (X = Cl 3, Br 4 or I 5). These complexes, which contain only one aminophosphine chelate, have a distorted-octahedral geometry, as evidenced by a crystal structure determination of 2. Reactions conducted in basic media, or treatment of 2 in the presence of the weakly co-ordinating trifluoromethanesulfonic acid, gave the bis(chelate) cationic complexes [ReO₂L₂]⁺6 and [ReCl₂L₂]⁺7, respectively. Similar ligand-exchange reactions between the lower-oxidation-state precursor [Re^IIICl₃(MeCN)(PPh₃)₂] and L or L′ [o-(diphenylphosphino)aniline] still produced mono-substituted aminophosphine complexes, i.e. [Re^IIICl₃L(PPh₃)] 8 or [Re^IIICl₃L′(PPh₃)] 9 in which there is a meridional arrangement of chloride ligands along with a cis-phosphorus co-ordination. The crystal structure of 8 was determined. On the contrary, treatment of [Re^IIIX₃(MeCN)(PPh₃)₂] (X = Cl or Br) with L′ in the presence of co-ordinating hydrohalogenic acid gave bis-substituted cationic complexes [ReX₂L′₂]⁺ (X = Cl 10 or Br 11). In spite of the paramagnetism of the low-spin d⁴ ion, all of the rhenium(III) complexes can be conveniently characterised in solution by proton NMR spectroscopy.

References

1. W. Keim, Angew. Chem., Int. Ed. Engl., 1990, 29, 235; M. C. Bonnet, F. Dahan, A. Ecke, W. Keim, R. P. Schultz and I. Tkachenko, J. Chem. Soc., Chem. Commun., 1994, 615; G. J. Britovsek, W. Keim, S. Mecking, D. Sainz and T. Wagner, J. Chem. Soc., Chem. Commun., 1993, 1632.
2. P. Braunstein, Y. Chauvin, S. Mercier, L. Saussine, A. DeCian and J. Fisher, J. Chem. Soc., Chem. Commun., 1994, 2203; P. Braunstein, J. Pietsch, Y. Chauvin, S. Mercier, L. Saussine, A. DeCian and J. Fisher, J. Chem. Soc., Dalton Trans., 1996, 3571.
3. A. Habtemariam and P. J. Sadler, Chem. Commun., 1996, 1785.
4. E. F. Lutz, J. Chem. Educ., 1986, 63, 202.
5. H. P. Fritz, I. R. Gordon, K. E. Schwarzhans and L. M. Venanzi, J. Chem. Soc., 1965, 5210.
6. H. P. Fritz and K. E. Schwarzhans, J. Organomet. Chem., 1966, 5, 103.
7. T. B. Rauchfuss, F. T. Patino and D. M. Roundhill, Inorg. Chem., 1975, 14, 652.
8. T. B. Rauchfuss and D. M. Roundhill, J. Am. Chem. Soc., 1974, 96, 3098.
9. D. M. Roundhill, R. A. Bechtold and S. Roundhill, Inorg. Chem., 1980, 19, 284.
10. D. C. Mudalige, S. J. Rettig, B. R. James and W. R. Cullen, J. Chem. Soc., Chem. Commun., 1993, 830.
11. E. Farnetti, G. Nardin and M. Graziani, J. Chem. Soc., Chem. Commun., 1989, 1264.
12. B. R. Martin, 31st ICCC Conference, Vancouver, 1996, abstract PL2, p. 4.
13. J. Reedijk, Chem. Commun., 1996, 801.
14. F. Refosco, C. Bolzati, A. Moresco, G. Bandoli, A. Dolmella, U. Mazzi and M. Nicolini, J. Chem. Soc., Dalton Trans., 1991, 3043.
15. F. Refosco, F. Tisato, G. Bandoli, C. Bolzati, A. Dolmella, A. Moresco and M. Nicolini, J. Chem. Soc., Dalton Trans., 1993, 605.
16. F. Refosco, F. Tisato, A. Moresco and G. Bandoli, J. Chem. Soc., Dalton Trans., 1995, 3475.
17. M. Nicolini, G. Bandoli and U. Mazzi, Technetium and Rhenium in Chemistry and Nuclear Medicine, GEditoriali, Padova, 1995, vol. 4.
18. F. Tisato, F. Refosco, A. Moresco, G. Bandoli, A. Dolmella and C. Bolzati, Inorg. Chem., 1995, 34, 1779.
19. G. D. Meakins and R. D. Hill, J. Chem. Soc., 1958, 229.
20. F. Tisato, C. Bolzati, A. Duatti, G. Bandoli and F. Refosco, Inorg. Chem., 1993, 32, 2042.
21. F. Tisato, F. Refosco, E. Deutsch and M. Nicolini, Technetium and Rhenium in Chemistry and Nuclear Medicine, eds. M. Nicolini, G. Bandoli and U. Mazzi, SGEditoriali, Padova, 1995, vol. 4, p. 155.
22. H. J. Keller and K. E. Schwarzhans, Angew. Chem., Int. Ed. Engl., 1970, 9, 196; R. R. Conry and J. M. Mayer, Inorg. Chem., 1990, 29, 4862; X. L. R. Fontaine, E. H. Fowles, T. P. Layzell, B. L. Shaw and M. Thornton-Pett, J. Chem. Soc., Dalton Trans., 1991, 1519; S. D. Orth, J. Barrera, M. Sabat and W. D. Harman, Inorg. Chem., 1993, 32, 594; L. E. Helberg, S. D. Orth, M. Sabat and W. D. Harman, Inorg. Chem., 1996, 35, 5584.
23. J. C. Bryan, R. E. Stenkamp, T. H. Tulip and J. M. Mayer, Inorg. Chem., 1987, 26, 2283.
24. R. R. Gagne, C. A. Koval and G. C. Lisensky, Inorg. Chem., 1980, 19, 2854.
25. J. R. Kirchoff, W. R. Heineman and E. Deutsch, Inorg. Chem., 1987, 26, 3108.
26. F. Refosco, F. Tisato, G. Bandoli and E. Deutsch, J. Chem. Soc., Dalton Trans., 1993, 2901.
27. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
28. S. C. Nyburg, Acta Crystallogr., Sect. B, 1974, 30, 251.
29. G. J. Organ, M. K. Cooper, K. Henrich and M. McPartlin, J. Chem. Soc., Dalton Trans., 1984, 2377.
30. M. K. Cooper, J. M. Downes, H. J. Goodwin and M. McPartlin, Inorg. Chim. Acta, 1983, 76, L157; M. K. Cooper, J. M. Downes, H. J. Goodwin, M. McPartlin and J. M. Rosalsky, Inorg. Chim. Acta, 1983, 76, L155.
31. L. Crociani, F. Refosco, F. Tisato, S. Gatto and B. Corain, Inorg. Chim. Acta, 1996, 249, 131.
32. L. Crociani, F. Refosco, F. Tisato, A. Dolmella, S. Gatto and G. Bandoli, Z. Kristallogr., submitted for publication.
33. G. Gritzner and J. Kuta, Electrochim. Acta, 1984, 29, 869.
34. G. Rouschias, Chem. Rev., 1974, 74, 531 and refs. therein.
35. T. B. Rauchfuss and D. M. Roundhill, J. Am. Chem. Soc., 1974, 96, 3098.
36. M. K. Cooper, J. M. Downes, P. A. Duckworth, M. C. Kerby, R. J. Powell and M. D. Soucek, Inorg. Synth., 1989, 25, 129.
37. G. M. Sheldrick, SHELXTL PLUS, version 4.2, Siemens Analytical Instruments, Madison, WI, 1990.
38. D. Rogers, Acta Crystallogr., Sect. A, 1981, 37, 734.
39. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351.