Pentamethylcyclopentadienyl tungsten complexes containing imido, hydrazido and amino acid derived N–O chelate ligands 

Abstract

Reactions of [W(η-C₅Me₅)Cl₄] with a number of functionalised amines have been studied. With 2 equivalents of the dianiline 2,2′-(H₂NC₆H₄)₂C ₂H₄ the ansa-bis(imido)tungsten complex [W(η-C₅Me₅)Cl{2,2′-(NC₆ H₄)₂CH₂CH₂}] 1 was obtained. Analogous treatment with 2-diphenylphosphinoaniline gave the 2-diphenylphosphine-substituted imidometal species [W(η-C₅Me₅)Cl(NC₆H₄PPh ₂-2)₂] 2. The pendant tertiary phosphine groups do not interact with the metal centre. 1,1-Diphenylhydrazine hydrochloride reacted with [W(η-C₅Me₅)Cl₄] to give [W(η-C₅Me₅)Cl₃(NNPh₂)] 3. Reactions of [W(η-C₅Me₅)Cl₄] with the amino acid 2,2-diphenylglycine or tyrosine afforded the tungsten(V) complexes [W(η-C₅Me₅)Cl₃(NH₂CPh ₂CO₂)] 4 and [W(η-C₅Me₅)Cl₃{NH₂ CH(CH₂C₆H₄OH-p)CO₂ }] 5 respectively. Complexes 1 to 5 have been structurally characterised.

References

1. D. E. Wigley, Prog. Inorg. Chem., 1994, 42, 239.
2. J. H. Oskam, H. H. Fox, K. B. Yap, D. H. McConville, R. O'Dell, B. J. Lichtenstein and R. R. Schrock, J. Organomet. Chem., 1993, 459, 185.
3. P. E. Collier, S. C. Dunn, P. Mountford, O. V. Shishkin and D. Swallow, J. Chem. Soc., Dalton Trans., 1995, 3743; A. J. Blake, P. E. Collier, S. C. Dunn, W.-S. Li, P. Mountford and O. V. Shishkin, J. Chem. Soc., Dalton Trans., 1997, 1549; M. L. H. Green, J. T. James and J. F. Saunders, Chem. Commun., 1996, 1345.
4. J. B. Arterburn, I. M. Fogarty, K. A. Hall, K. C. Ott and J. C. Bryan, Angew. Chem., Int. Ed. Engl., 1996, 35, 2877.
5. V. C. Gibson, C. Redshaw, W. Clegg and M. R. J. Elsegood, J. Chem. Soc., Dalton Trans., 1997, 18, 3207.
6. V. C. Gibson, C. Redshaw, W. Clegg, M. R. J. Elsegood, U. Siemeling and T. Turk, J. Chem. Soc., Dalton Trans., 1996, 4513.
7. (a) C. Redshaw, G. Wilkinson, T. K. N. Sweet and M. B. Hursthouse, Polyhedron, 1993, 12, 2417; (b) J. Okuda, R. C. Murray, J. C. Dewan and R. R. Schrock, Organometallics, 1986, 5, 1681; (c) A. H. Liu, R. C. Murray, B. D. Santarsiero and R. R. Schrock, J. Am. Chem. Soc., 1987, 109, 4282; (d) C. J. Harlan, R. A. Jones, S. U. Koschmieder and C. M. Nunn, Polyhedron, 1990, 9, 669; (e) M. S. Rau, C. M. Kretz, L. A. Mercando and G. L. Geoffrey, J. Am. Chem. Soc., 1991, 113, 7420; (f) M. B. O'Regan, M. G. Vale, J. F. Payack and R. R. Schrock, Inorg. Chem., 1992, 31, 1112.
8. (a) J. Sundemeyer, U. Radius and C. Burschka, Chem. Ber., 1992, 125, 2379; (b) M. L. H. Green, P. C. Konidaris, P. Mountford and S. J. Simpson, J. Chem. Soc., Chem. Commun., 1992, 256.
9. S. R. Huber, T. C. Baldwin and D. E. Wigley, Organometallics, 1993, 12, 91.
10. M. T. Ahmet, B. Coutinho, J. R. Dilworth, J. R. Miller, S. J. Parrott, Y. Zheng, M. Harman, M. B. Hursthouse and A. Malik, J. Chem. Soc., Dalton Trans., 1995, 3041.
11. J. R. Dilworth, V. C. Gibson, C. Lu, J. R. Miller, C. Redshaw and Y. Zhend, J. Chem. Soc., Dalton Trans., 1996, 269; A. A. Danopoulos, G. Wilkinson and D. J. Williams, J. Chem. Soc., Dalton Trans., 1994, 907.
12. See, for example, W. A. Herrmann, U. Küsthardt and E. Herdtweck, J. Organomet. Chem., 1985, 294, C37; R. D. Sanner, S. T. Carter and W. J. Bruton, jun., J. Organomet. Chem., 1982, 240, 157.
13. M. K. Cooper, J. M. Downes, P. A. Duckworth, M. C. Kerby, R. J. Powell and M. D. Soucek, Inorg. Synth., 1989, 25, 129.
14. R. C. Murrey, L. Blum, A. H. Liu and R. R. Schrock, Organometallics, 1985, 4, 953.
15. G. M. Sheldrick, SHELXTL PLUS, Siemens Analytical Instruments, Madison, WI, 1990.