Synthesis and imido-group exchange reactions of tert-butylimidotitanium complexes

Abstract

Treatment of TiCl₄ with Bu^tNH₂ (6 equivalents) followed by addition of bpy (2 equivalents, 4-tert-butylpyridine) or pyridine (py) (2 or 4 equivalents) afforded the five- or six-co-ordinate tert-butylimido complexes [Ti(NBu^t)Cl₂(bpy)₂] or [Ti(NBu^t)Cl₂(py)_n] (n = 2 or 3*) respectively in good yields. Reaction of [Ti(NBu^t)Cl₂(py)₃] with RNH₂ gave the corresponding arylimido derivatives [Ti(NR)Cl₂(py)₃] (R = Ph,* C₆H₄Me-4,* C₆H₄NO₂-4,* C₆H₃Me₂-2,6 or C₆H₃Prⁱ₂-2,6). Addition of tmen or pmdien to [Ti(NBu^t)Cl₂(py)_n] (n = 2 or 3 respectively) gave the corresponding bi- or tri-dentate amine complexes, [Ti(NBu^t)Cl₂(tmen)] or [Ti(NBu^t)Cl₂(pmdien)]* (tmen = Me₂NCH₂CH₂NMe ₂, pmdien = N,N,N′,N ″,N ″ -pentamethyldiethylenetriamine). Complexes labelled * have been crystallographically characterised.

References

1. D. E. Wigley, Prog. Inorg. Chem., 1994, 42, 239.
2. W. A. Nugent and J. M. Mayer, Metal-Ligand Multiple Bonds, Wiley-Interscience, New York, 1988.
3. W. A. Nugent and B. L. Haymore, Coord. Chem. Rev., 1980, 31, 123.
4. V. C. Gibson, Adv. Mater., 1994, 6, 37.
5. J. E. Hill, R. D. Profilet, P. E. Fanwick and I. P. Rothwell, Angew. Chem., Int. Ed. Engl., 1990, 29, 664.
6. H. W. Roesky, H. Voelker, M. Witt and M. Noltemeyer, Angew. Chem., Int. Eng. Engl., 1990, 29, 669.
7. S. C. Dunn, A. S. Batsanov and P. Mountford, J. Chem. Soc., Chem. Commun., 1994, 2007.
8. P. Mountford and D. Swallow, J. Chem. Soc., Chem. Commun., 1995, 2357.
9. K. A. Butakoff, D. A. Lemenovskii, P. Mountford, L. G. Kuz'mina and A. V. Churakov, Polyhedron, 1996, 15, 489.
10. S. C. Dunn, P. Mountford and O. V. Shishkin, Inorg. Chem., 1996, 35, 1006.
11. S. C. Dunn, P. Mountford and D. A. Robson, J. Chem. Soc., Dalton Trans., 1997, 293.
12. P. E. Collier, S. C. Dunn, P. Mountford, O. V. Shishkin and D. Swallow, J. Chem. Soc., Dalton Trans., 1995, 3743.
13. R. T. Cowdell and G. W. A. Fowles, J. Chem. Soc., 1960, 2522.
14. A. J. Nielson, Inorg. Chim. Acta, 1988, 154, 177.
15. T. S. Lewkebandara, P. H. Sheridan, M. J. Heeg, A. L. Rheingold and C. H. Winter, Inorg. Chem., 1994, 33, 5879.
16. R. Mason and A. D. C. Towl, J. Chem. Soc. A, 1970, 1601.
17. J. K. Burdett and T. A. Albright, Inorg. Chem., 1979, 18, 2112.
18. D. Bright and J. A. Ibers, Inorg. Chem., 1969, 8, 709.
19. E. M. Shustorovich, M. A. Porai-Koshits and Y. A. Buslaev, Coord. Chem. Rev., 1975, 17, 1.
20. K. Dehnicke and J. Strähle, Angew. Chem., Int. Ed. Engl., 1981, 20, 413.
21. W. P. Griffith, A. J. Nielson and M. J. Taylor, J. Chem. Soc., Dalton Trans., 1988, 647.
22. J. H. Osborne, A. L. Rheingold and W. C. Trogler, J. Am. Chem. Soc., 1985, 107, 7945.
23. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley, New York, 4th edn., 1986.
24. P. E. Collier, A. J. Blake and P. Mountford, unpublished work.
25. C. H. Winter, P. H. Sheridan, T. S. Lewkebandara, M. J. Heeg and J. W. Proscia, J. Am. Chem. Soc., 1992, 114, 1095.
26. R. Duchateau, A. J. Williams, S. Gambarotta and M. Y. Chiang, Inorg. Chem., 1991, 30, 4863.
27. H. W. Roesky, T. Raubold, M. Witt, R. Bohra and M. Noltemeyer, Chem. Ber., 1991, 124, 1521.
28. H. Burger and U. Wannagat, Monatsh. Chem., 1963, 94, 761.
29. D. J. Arney, M. A. Bruck, S. R. Huber and D. E. Wigley, Inorg. Chem., 1992, 31, 3749.
30. M. P. Coles, C. I. Dalby, V. C. Gibson, W. Clegg and M. R. J. Elsegood, Polyhedron, 1995, 14, 2455.
31. A. Bell, W. Clegg, P. W. Dyer, M. R. J. Elsegood, V. C. Gibson and E. L. Marshall, J. Chem. Soc., Chem. Commun., 1994, 2247.
32. A. Bell, W. Clegg, P. W. Dyer, M. R. J. Elsegood, V. C. Gibson and E. L. Marshall, J. Chem. Soc., Chem. Commun., 1994, 2547.
33. R. I. Michelman, R. G. Bergman and R. A. Andersen, Organometallics, 1993, 12, 2741.
34. D. S. Glueck, J. Wu, F. J. Hollander and R. G. Bergman, J. Am. Chem. Soc., 1991, 113, 2041.
35. P. D. Lyne and D. M. P. Mingos, J. Chem. Soc., Dalton Trans., 1995, 1635.
36. P. D. Lyne and D. M. P. Mingos, J. Organomet. Chem., 1994, 478, 141.
37. R. C. B. Copley, P. W. Dyer, V. C. Gibson, J. A. K. Howard, E. L. Marshall, W. Wang and B. Whittle, Polyhedron, 1996, 15, 3001.
38. W. Clegg, R. J. Errington, D. C. R. Hockless and C. Redshaw, J. Chem. Soc., Dalton Trans., 1993, 1965.
39. D. Bright and J. A. Ibers, Inorg. Chem., 1969, 8, 703.
40. D. Bright and J. A. Ibers, Inorg. Chem., 1968, 7, 1099.
41. C. Y. Chou, J. C. Huffman and E. A. Maatta, Inorg. Chem., 1986, 25, 822.
42. D. C. Bradley, R. J. Errington, M. B. Hursthouse and R. L. Short, J. Chem. Soc., Dalton Trans., 1990, 1043.
43. B. R. Ashcroft, G. R. Clark, A. J. Nielson and C. E. F. Rickard, Polyhedron, 1986, 5, 2081.
44. W. Clegg and R. J. Errington, Acta Crystallogr., Sect. C, 1987, 43, 2223.
45. K. Stahl, F. Weller, K. Dehnicke and P. Paetzold, Z. Anorg. Allg. Chem., 1986, 534, 93.
46. A. Bell, personal communication cited in ref. 1.
47. D. N. 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.
48. G. H. Stout and L. H. Jensen, X-Ray Structure Determination, Wiley, Toronto, 2nd edn., 1989.
49. J. Chatt, J. D. Garforth, N. P. Johnson and G. A. Rowe, J. Chem. Soc., 1964, 1012.
50. F. H. Allen and O. Kennard, Chem. Design Autom. News, 1993, 8, 1.
51. D. A. Fletcher, R. F. McMeeking and D. Parkin, J. Chem. Inf. Comput. Sci., 1996, 36, 746.
52. A. Bodner, P. Jeske, T. Weyhermüller, K. Wieghardt, E. Dubler, H. Schmalle and B. Nuber, Inorg. Chem., 1992, 31, 3737.
53. P. Jeske, G. Haselhorst, T. Weyhermüller, K. Wieghardt and B. Nuber, Inorg. Chem., 1994, 33, 2462.
54. J. Cosier and A. M. Glazer, J. Appl. Crystallogr., 1986, 19, 105.
55. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
56. G. M. Sheldrick, SHELXL 96, Institut für Anorganische Chemie der Universität Göttingen, 1996.