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DOI: 10.1039/A705374F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 301-310

Boron–boron bond oxidative addition to rhodium(I) and iridium(I) centres

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William Clegg, Fiona J. Lawlor, Todd B. Marder, Paul Nguyen, Nicholas C. Norman, A. Guy Orpen, Michael J. Quayle, Craig R. Rice, Edward G. Robins, Andrew J. Scott, Fabio E. S. Souza, Graham Stringer and George R. Whittell

Abstract

The reaction between the diborane(4) compound B2(1,2-O2C6H4)2 and either of the rhodium(I) complexes [RhCl(PPh3)3] or [{Rh(µ-Cl)(PPh3)2}2] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh3)2{B(1,2-O2C6H4)}2]. Similar reactions have been carried out with the diborane(4) compounds B2(1,2-O2-4-ButC6H3)2, B2(1,2-O2-3,5-But2C6H2)2, B2(1,2-O2-3-MeC6H3)2, B2(1,2-O2-4-MeC6H3)2, B2(1,2-O2-3-MeOC6H3)2, B2(1,2-S2C6H4)2, B2(1,2-S2-4-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO2Me)]2 affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B2(1,2-O2C6H4)2 and B2(1,2-O2-3-MeC6H3)2 have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trans in basal positions. Reactivity studies have also been carried out for [RhCl(PPh3)2{B(1,2-O2C6H4)}2]. Hydrolysis or alcoholysis with catechol afforded [RhH2Cl(PPh3)3] and either B2(1,2-O2C6H4)2(µ-O) or B2(1,2-O2C6H4)3 and addition of the phosphines PMe3, PEt3 and PMe2Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe3)3{B(1,2-O2C6H4)}2], [RhCl(PEt3)2{B(1,2-O2C6H4)}2] and cis,mer-[RhCl(PMe2Ph)3{B(1,2-O2C6H4)}2], the PEt3 complex having been characterised by X-ray crystallography and shown to be similar to the PPh3 complex. The iridium analogue [IrCl(PEt3)2{B(1,2-O2C6H4)}2] was also prepared from the reaction between [IrCl(PEt3)3] and B2(1,2-O2C6H4)2 and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh3)2{B(1,2-O2C6H4)}2] and the phosphines PPri3, P(C6H11)3, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [{RhCl(dppe)}2] and B2(1,2-O2C6H4)2 afforded a compound tentatively assigned as [Rh(dppe)2{B(1,2-O2C6H4)}] with analogous compounds being formed with the diborane(4) compounds B2(1,2-O2-3-MeC6H3)2 and B2(1,2-O2-4-MeC6H3)2. Finally, the reaction between [Rh(PMe3)4]Cl and the diborane(4) compound B2(1,2-O2C6H4)2 is described which affords cis,mer-[RhCl(PMe3)3{B(1,2-O2C6H4)}2]. Analogous reactions with B2(1,2-O2-3,5-But2C6H2)2, B2(1,2-O2-3-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO2Me)]2 afforded similar products.

References

  1. R. T. Baker, P. Nguyen, T. B. Marder and S. A. Westcott, Angew. Chem., Int. Ed. Engl., 1995, 34, 1336 CrossRef CAS; T. Ishiyama, M. Yamamoto and N. Miyaura, Chem. Commun., 1997, 689 RSC; C. N. Iverson and M. R. Smith, Organometallics, 1997, 16, 2757 CrossRef CAS.
  2. (a) T. Ishiyama, N. Matsuda, N. Miyaura and A. Suzuki, J. Am. Chem. Soc., 1993, 115, 11018 CrossRef CAS; (b) T. Ishiyama, N. Matsuda, M. Murata, F. Ozawa, A. Suzuki and N. Miyaura, Organometallics, 1996, 15, 713 CrossRef; (c) C. N. Iverson and M. R. Smith, J. Am. Chem. Soc., 1995, 117, 4403 CrossRef CAS; (d) C. N. Iverson and M. R. Smith, Organometallics, 1996, 15, 5155 CrossRef CAS; (e) G. Lesley, P. Nguyen, N. J. Taylor, T. B. Marder, A. J. Scott, W. Clegg and N. C. Norman, Organometallics, 1996, 15, 5137 CrossRef; (f) W. Clegg, F. J. Lawlor, G. Lesley, T. B. Marder, N. C. Norman, A. G. Orpen, M. J. Quayle, C. R. Rice, A. J. Scott and F. E. S. Souza, J. Organomet. Chem., 1997, in the press Search PubMed.
  3. T. Ishiyama, M. Yamamoto and N. Miyaura, Chem. Commun., 1996, 2073 RSC.
  4. T. Ishiyama, M. Murata and N. Miyaura, J. Org. Chem., 1995, 60, 7508 CrossRef CAS; T. Ishiyama, M. Yamamoto and N. Miyaura, Chem. Lett., 1996, 1117 CAS.
  5. J. F. Hartwig and X. He, Angew. Chem., Int. Ed. Engl., 1996, 35, 315 CrossRef CAS; Organometallics, 1996, 15, 5350 Search PubMed.
  6. X. He and J. F. Hartwig, Organometallics, 1996, 15, 400 CrossRef CAS.
  7. C. Dai, G. Stringer, J. F. Corrigan, N. J. Taylor, T. B. Marder and N. C. Norman, J. Organomet. Chem., 1996, 513, 273 CrossRef CAS.
  8. (a) P. Nguyen, G. Lesley, N. J. Taylor, T. B. Marder, N. L. Pickett, W. Clegg, M. R. J. Elsegood and N. C. Norman, Inorg. Chem., 1994, 33, 4623 CrossRef CAS; (b) R. T. Baker, J. C. Calabrese, S. A. Westcott, P. Nguyen and T. B. Marder, J. Am. Chem. Soc., 1993, 115, 4367 CrossRef CAS; (c) C. Dai, G. Stringer, T. B. Marder, A. J. Scott, W. Clegg and N. C. Norman, Inorg. Chem., 1997, 36, 272 CrossRef CAS.
  9. C. Dai, G. Stringer, T. B. Marder, R. T. Baker, A. J. Scott, W. Clegg and N. C. Norman, Can. J. Chem., 1996, 74, 2026 CAS.
  10. D. R. Lantero, D. H. Motry, D. L. Ward and M. R. Smith, J. Am. Chem. Soc., 1994, 116, 10811 CrossRef CAS.
  11. J. F. Hartwig and S. R. De Gala, J. Am. Chem. Soc., 1994, 116, 3661 CrossRef CAS.
  12. K. M. Waltz, X. He, C. Muhoro and J. F. Hartwig, J. Am. Chem. Soc., 1995, 117, 11357 CrossRef CAS.
  13. J. F. Hartwig and S. Huber, J. Am. Chem. Soc., 1993, 115, 4908 CrossRef CAS.
  14. S. A. Westcott, N. J. Taylor, T. B. Marder, R. T. Baker, N. J. Jones and J. C. Calabrese, J. Chem. Soc., Chem. Commun., 1991, 304 RSC.
  15. S. A. Westcott, T. B. Marder, R. T. Baker and J. C. Calabrese, Can. J. Chem., 1993, 71, 930 CAS; P. Nguyen, H. P. Blom, S. A. Westcott, N. J. Taylor and T. B. Marder, J. Am. Chem. Soc., 1993, 115, 9329 CrossRef CAS; J. R. Knorr and J. S. Merola, Organometallics, 1990, 9, 3008 CrossRef CAS; R. T. Baker, D. W. Ovenall, J. C. Calabrese, S. A. Westcott, N. J. Taylor, I. D. Williams and T. B. Marder, J. Am. Chem. Soc., 1990, 112, 9399 CrossRef CAS.
  16. (a) F. J. Lawlor, N. C. Norman, N. L. Pickett, E. G. Robins, P. Nguyen, G. Lesley, T. B. Marder, J. A. Ashmore and J. C. Green, Inorg. Chem., in the press Search PubMed; (b) W. Clegg, M. R. J. Elsegood, F. J. Lawlor, N. C. Norman, N. L. Pickett, E. G. Robins, A. J. Scott, P. Nguyen, N. J. Taylor and T. B. Marder, Inorg. Chem., in the press Search PubMed.
  17. N. C. Norman and C. R. Rice, unpublished work.
  18. C. Dai, G. Lesley, T. B. Marder, N. C. Norman, C. R. Rice, E. G. Robins, W. R. Roper, F. E. S. Souza and G. R. Whittell, Chem. Rev., manuscript in preparation Search PubMed.
  19. G. Lesley, T. B. Marder, N. C. Norman and C. R. Rice, Main Group Chem. News, 1997, 5, 4 Search PubMed.
  20. S. Sakaki and T. Kikuno, Inorg. Chem., 1997, 36, 226 CrossRef CAS; Q. Cui, D. G. Musaev and K. Morokuma, Organometallics, 1997, 16, 1355 CrossRef CAS.
  21. I. El-Idrissi Rachidi, O. Eisenstein and Y. Jean, New J. Chem., 1990, 14, 671 Search PubMed; J.-F. Riehl, Y. Jean, O. Eisenstein and M. Pélissier, Organometallics, 1992, 11, 729 CrossRef CAS.
  22. K. Burgess, W. A. van der Donk, S. A. Westcott, T. B. Marder, R. T. Baker and J. C. Calabrese, J. Am. Chem. Soc., 1992, 114, 9350 CrossRef CAS.
  23. (a) A. Sacco, R. Ugo and A. Moles, J. Chem. Soc. A, 1966, 1670 RSC; (b) W. MacFarlane, N. C. Norman and N. L. Pickett, unpublished work.
  24. W. Gerrard, M. F. Lappert and B. A. Mountfield, J. Chem. Soc., 1959, 1529 RSC.
  25. S. A. Westcott, H. P. Blom, T. B. Marder, R. T. Baker and J. C. Calabrese, Inorg. Chem., 1993, 32, 2175 CrossRef CAS.
  26. W. Clegg, T. B. Marder, N. C. Norman, N. L. Pickett, E. G. Robins and A. J. Scott, Acta Crystallogr., Sect. C, manuscript in preparation and refs. therein Search PubMed.
  27. G. J. Irvine, W. R. Roper and L. J. Wright, Organometallics, 1997, 16, 2291 CrossRef CAS.
  28. T. B. Marder, W. C. Fultz, J. C. Calabrese, R. L. Harlow and D. Milstein, J. Chem. Soc., Chem. Commun., 1987, 1543 RSC.
  29. B. Bogdanovic, W. Leitner, C. Six, U. Wilczok and K. Wittmann, Angew. Chem., Int. Ed. Engl., 1997, 36, 502 CrossRef CAS.
  30. W. Clegg, M. R. J. Elsegood, T. B. Marder, N. C. Norman, N. L. Pickett, E. G. Robins and A. J. Scott, Acta Crystallogr., Sect. C, in preparation Search PubMed.
  31. T. B. Marder, unpublished work.
  32. J. A. Osborn, G. Wilkinson and J. J. Mrowca, Inorg. Synth., 1972, 10, 67.
  33. R. A. Jones, F. M. Real, G. Wilkinson, A. M. R. Galas, M. B. Hursthouse and K. M. A. Malik, J. Chem. Soc., Dalton Trans., 1980, 511 RSC.
  34. J. R. Bleeke and W.-J. Peng, Organometallics, 1987, 6, 1576 CrossRef CAS ; see also A. van der Ent and A. L. Onderdelinden, Inorg. Synth., 1990, 28, 91 Search PubMed.
  35. D. P. Fairlie and B. Bosnich, Organometallics, 1988, 7, 936 CrossRef CAS.
  36. SMART (control) and SAINT (integration) software, Siemens Analytical X-Ray Instruments Inc., Madison, WI, 1994.
  37. G. M. Sheldrick, SHELXTL version 5, Siemens Analytical X-Ray Instruments Inc., Madison, WI, 1995.
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