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DOI: 10.1039/A803941K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2451-2458

Bridge to terminal migration and ring closure in a dimolybdenum metallacyclopentadiene complex

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Harry Adams, Louise J. Gill and Michael J. Morris

Abstract

The dinuclear complex [Mo2(O)(µ-O)(µ-C4Ph4)(η-C5H5)2] 2a reacted with PhNCO in refluxing toluene to give [Mo2(O)(µ-NPh)(µ-C4Ph4)(η-C5H5)2] 3a. A crystal structure determination of the η-C5H4Me analogue 3b revealed that the bridging C4Ph4 ligand displays an unprecedented bonding mode in which one terminus bridges the two metal atoms whereas the other is bonded to only one molybdenum in the manner of a terminal alkylidene. Owing to the similarity of the 13C NMR spectra of 2a and 3a, we now propose that this bonding mode is also present in the former, and that the ligand rearrangement occurs during the air oxidation of the metallacyclopentadiene complex [Mo2(CO)(µ-C4Ph4)(η-C5H5)2] 1 to form 2a. The reaction of 2a with PriSH afforded an analogous sulfido complex, [Mo2(S)(µ-O)(µ-C4Ph4)(η-C5H5)2] 4a. A second product of this reaction was identical to that formed by treatment of 2 with elemental sulfur and had the formula [Mo2(O)(µ-O)(µ-S)(η-C4Ph4)(η-C5H5)2] 5a. The crystal structure of the analogous complex [Mo2(O)(µ-O)(µ-S)(η-C4tol4)(η-C5H4Me)2] 5d was determined, and confirmed that the C4R4 ligand had closed up into an η4-cyclobutadiene ring. This sequence of reactions therefore represents the gradual migration of the bridging metallacyclopentadiene unit partially (in 2 or 3) or wholly (in 5) onto one molybdenum atom, a process believed to be sterically driven.

References

  1. W. A. Nugent and J. M. Meyer, Metal-Ligand Multiple Bonds, Wiley Interscience, New York, 1988 Search PubMed; D. E. Wigley, Prog. Inorg. Chem., 1994, 42, 239 Search PubMed; F. Bottomley and L. Sutin, Adv. Organomet. Chem., 1988, 28, 339 CAS; C. C. Romão, F. E. Kühn and W. A. Herrmann, Chem. Rev., 1997, 97, 3197 CAS.
  2. P. Blenkiron, A. J. Carty, S.-M. Peng, G.-H. Lee, S.-J. Su, C.-W. Shiu and Y. Chi, Organometallics, 1997, 16, 519 CrossRef CAS; C.-W. Shiu, Y. Chi, A. J. Carty, S.-M. Peng and G.-H. Lee, Organometallics, 1997, 16, 5368 CrossRef CAS; H. G. Alt, H. I. Hayen and R. D. Rogers, J. Chem. Soc., Chem. Commun., 1987, 1795 RSC.
  3. F. Bottomley, C. P. Magill and B. Zhao, Organometallics, 1991, 10, 1946 CrossRef CAS.
  4. F. Bottomley, P. D. Boyle and J. Chen, Organometallics, 1994, 13, 370 CrossRef CAS; W. A. Herrmann, E. Voss and M. Flöel, J. Organomet. Chem., 1985, 297, C5 CrossRef CAS.
  5. J. C. Stichbury, M. J. Mays, J. E. Davies, P. R. Raithby and G. P. Shields, J. Chem. Soc., Dalton Trans., 1997, 2309 RSC.
  6. S. A. R. Knox, R. F. D. Stansfield, F. G. A. Stone, M. J. Winter and P. Woodward, J. Chem. Soc., Dalton Trans., 1982, 173 RSC; see also M. J. Winter, Ph.D. Thesis, University of Bristol, 1978.
  7. H. Adams, L. J. Gill and M. J. Morris, J. Chem. Soc., Chem. Commun., 1995, 899, 1309 RSC; Organometallics, 1996, 15, 4182 Search PubMed.
  8. H. Adams, L. J. Gill and M. J. Morris, J. Chem. Soc., Dalton Trans., 1996, 3909 RSC.
  9. H. Adams, L. J. Gill and M. J. Morris, J. Organomet. Chem., 1997, 533, 117 CrossRef CAS.
  10. M. L. H. Green and K. J. Moynihan, Polyhedron, 1986, 5, 921 CrossRef CAS; M. L. H. Green, G. Hogarth, P. C. Konidaris and P. Mountford, J. Chem. Soc., Dalton Trans., 1990, 3781 RSC; J. Fletcher, G. Hogarth and D. A. Tocher, J. Organomet. Chem., 1991, 403, 345 CrossRef CAS.
  11. T. A. Budzichowski, M. H. Chisholm and K. Folting, Chem. Eur. J., 1996, 2, 110 CrossRef CAS.
  12. A. F. Dyke, S. A. R. Knox, M. J. Morris and P. J. Naish, J. Chem. Soc., Dalton Trans., 1983, 1417 RSC; J. A. Beck, S. A. R. Knox, G. H. Riding, G. E. Taylor and M. J. Winter, J. Organomet. Chem., 1980, 202, C49 CrossRef CAS; P. O. Nubel and T. L. Brown, J. Am. Chem. Soc., 1982, 104, 4955 CrossRef CAS; J. A. Iggo, M. J. Mays, P. R. Raithby and K. Henrick, J. Chem. Soc., Dalton Trans., 1983, 205 RSC.
  13. J. L. Kiplinger and T. G. Richmond, Polyhedron, 1997, 16, 409 CrossRef CAS; J. L. Kiplinger, T. G. Richmond, A. M. Arif, C. Dücker-Benfer and R. van Eldik, Organometallics, 1996, 15, 1545 CrossRef CAS; J. L. Kiplinger, M. A. King, A. M. Arif and T. G. Richmond, Organometallics, 1993, 12, 3382 CrossRef CAS; S. G. Feng and J. L. Templeton, Organometallics, 1992, 11, 2168 CrossRef CAS; S. G. Feng, A. S. Gamble and J. L. Templeton, Organometallics, 1989, 8, 2024 CrossRef CAS; A. S. Gamble, P. S. White and J. L. Templeton, Organometallics, 1991, 10, 693 CrossRef CAS; S. R. Allen, R. G. Beevor, M. Green, N. C. Norman, A. G. Orpen and I. D. Williams, J. Chem. Soc., Dalton Trans., 1985, 435 RSC; L. Carlton and J. L. Davidson, J. Chem. Soc., Dalton Trans., 1987, 895 RSC; N. M. Agh-Atabay, L. J. Canoira, L. Carlton and J. L. Davidson, J. Chem. Soc., Dalton Trans., 1991, 1175 RSC.
  14. W. Hübel, in Organic Syntheses via Metal Carbonyls, eds. I. Wender and P. Pino, Wiley Interscience, New York, 1968, p. 273 Search PubMed.
  15. W. Hirpo and M. D. Curtis, J. Am. Chem. Soc., 1988, 110, 5218 CrossRef CAS; M. C. Milletti and M. D. Curtis, Polyhedron, 1990, 9, 1855 CrossRef CAS.
  16. M. L. H. Green and P. Mountford, Chem. Soc. Rev., 1992, 21, 29 RSC.
  17. A. A. Koridze, N. M. Astakhova, F. M. Dolgushin, A. I. Yanovsky, Y. T. Struchkov and P. V. Petrovskii, Organometallics, 1995, 14, 2167 CrossRef CAS.
  18. L. Messerle and M. D. Curtis, J. Am. Chem. Soc., 1982, 104, 889 CrossRef CAS.
  19. E. L. Muetterties and S. Slater, Inorg. Chem., 1981, 20, 946 CrossRef CAS.
  20. H. Adams, N. A. Bailey, A. P. Bisson and M. J. Morris, J. Organomet. Chem., 1993, 444, C34 CrossRef CAS; H. Adams, N. A. Bailey, S. R. Gay, T. Hamilton and M. J. Morris, J. Organomet. Chem., 1995, 493, C25 CrossRef CAS; H. Adams, N. A. Bailey, S. R. Gay, L. J. Gill, T. Hamilton and M. J. Morris, J. Chem. Soc., Dalton Trans., 1996, 2403 RSC; H. Adams, N. A. Bailey, M. N. Bancroft, A. P. Bisson and M. J. Morris, J. Organomet. Chem., 1997, 542, 131 CrossRef CAS.
  21. J. Fletcher, G. Hogarth and D. A. Tocher, J. Organomet. Chem., 1991, 405, 207 CrossRef CAS.
  22. O. J. Curnow, W. Hirpo, W. M. Butler and M. D. Curtis, Organometallics, 1992, 12, 4479.
  23. A. Abbott, M. N. Bancroft, M. J. Morris, G. Hogarth and S. P. Redmond, Chem. Commun., 1998, 389 RSC.
  24. J. A. Potenza, R. J. Johnson, R. Chirico and A. Efraty, Inorg. Chem., 1977, 16, 2354 CrossRef CAS; A. Efraty, Chem. Rev., 1977, 77, 691 CrossRef CAS; P. M. Maitlis, Adv. Organomet. Chem., 1966, 4, 95 CAS.
  25. M. O. Albers, P. J. A. deWaal, D. C. Liles, D. J. Robinson, E. Singleton and M. B. Wiege, J. Chem. Soc., Chem. Commun., 1986, 1680 RSC; M. D. Curtis, J. Real, W. Hirpo and W. M. Butler, Organometallics, 1990, 9, 66 CrossRef CAS.
  26. H. Adams, L. J. Gill and M. J. Morris, Organometallics, 1996, 15, 464 CrossRef CAS.
  27. H. Adams, N. A. Bailey, L. J. Gill, M. J. Morris and F. A. Wildgoose, J. Chem. Soc., Dalton Trans., 1996, 1437 RSC.
  28. R. Adams and C. S. Marvel, Org. Synth., 1932, Coll. Vol. 1, 94; H. T. Clarke and E. E. Dreger, Org. Synth., 1932, Coll. Vol. 1, 87; R. Popielarz and D. R. Arnold, J. Am. Chem. Soc., 1990, 112, 3068 CrossRef CAS; A. C. Cope, D. S. Smith and R. J. Cotter, Org. Synth., 1963, Coll. Vol. 4, 377.
  29. R. B. King, Organometallic Syntheses, Academic Press, New York, 1965, vol. 1, p. 109 Search PubMed.
  30. A. R. Manning, P. Hackett, R. Birdwhistell and P. Soye, Inorg. Synth., 1990, 28, 148 CAS.
  31. G. M. Sheldrick, SHELXL 93, An integrated system for solving and refining crystal structures from diffraction data, University of Göttingen, 1993.
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