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DOI: 10.1039/A810006C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1687-1694

Phosphine exchange reactions involving cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the oxidative addition of 1,2-B2Cl2(NMe2)2 to Pt0

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David Curtis, M. J. Gerald Lesley, Nicholas C. Norman, A. Guy Orpen and Jonathan Starbuck

Abstract

The reaction between the platinum(II) bis(boryl) complex cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the tertiary phosphines PMe3, PEt3, PMe2Ph, PMePh2 and dcpe [1,2-bis(dicyclohexylphosphino)ethane] and the phosphite P(OEt)3 afforded the new complexes cis-[Pt(PR3)2(Bcat)2] (PR3 = PMe3, PEt3, PMe2Ph or PMePh2), cis-[Pt(dcpe)(Bcat)2] and cis-[Pt{P(OEt)3}2(Bcat)2]. With PCy3 the mixed phosphine species cis-[Pt(PCy3)(PPh3)(Bcat)2] is the major product and was characterised by X-ray crystallography. With P(OMe)3 reductive elimination of B2(cat)2 and the formation of platinum(>0>) products occurs exclusively whereas with dmpe [1,2-bis(dimethylphosphino)ethane] the only identifiable product is the platinum(II) species [Pt(dmpe)2]Cl2. With dppm [bis(diphenylphosphino)methane] a reaction occurs to give a product assigned the structure cis-[Pt(dppm)(Bcat)2] or [Pt2(dppm)2(Bcat)4] but two binuclear products were isolated as minor products, namely [Pt2(PPh3)(µ-dppm)2(Bcat)(µ-Bcat)] and [Pt2(κ1-dppm)(µ-dppm)2(Bcat)(µ-Bcat)]. Both compounds were characterised by X-ray crystallography and shown to contain unusual semi-bridging Bcat groups. The reaction between [Pt(PPh3)2(η-C2H4)] and the diborane(4) compound 1,2-B2Cl2(NMe2)2 is also described which results in B–B bond oxidative addition yielding cis-[Pt(PPh3)2{BCl(NMe2)}2] and a complex to which this bis(boryl) subsequently rearranges, namely trans-[PtCl(PPh3)2{BCl(NMe2)}]. Both of these complexes were characterised by X-ray crystallography and have geometries typical of cis-bis(boryl) and trans-boryl chloride complexes respectively.

References

  1. 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; T. B. Marder, N. C. Norman and C. R. Rice, Tetrahedron Lett., 1998, 39, 155 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) A. Maderna, H. Pritzkow and W. Siebert, Angew. Chem., Int. Ed. Engl., 1995, 35, 1501 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) C. N. Iverson and M. R. Smith, Organometallics, 1996, 15, 5155 CrossRef CAS.
  3. (a) T. Ishiyama, M. Yamamoto and N. Miyaura, Chem. Commun., 1996, 2073 RSC; (b) W. Clegg, T. R. F. Johann, T. B. Marder, N. C. Norman, A. G. Orpen, T. M. Peakman, M. J. Quayle, C. R. Rice and A. J. Scott, J. Chem. Soc., Dalton Trans., 1998, 1431 RSC.
  4. Y. G. Lawson, M. J. G. Lesley, T. B. Marder, N. C. Norman and C. R. Rice, Chem. Commun., 1997, 2051 RSC.
  5. T. Ishiyama, T. Kitano and N. Miyaura, Tetrahedron Lett., 1998, 39, 2357 CrossRef CAS.
  6. 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.
  7. 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., 1998, 550, 183 CrossRef CAS.
  8. A. Kerr, T. B. Marder, N. C. Norman, A. G. Orpen, M. J. Quayle, C. R. Rice, P. L. Timms and G. R. Whittell, Chem. Commun., 1998, 319 RSC.
  9. (a) H. Wadepohl, Angew. Chem., Int. Ed. Engl., 1997, 36, 2441 CrossRef CAS; (b) T. B. Marder and N. C. Norman, Topics in Catalysis, eds. W. Leitner and D. G. Blackmond, Baltzer Science Publishers, Amsterdam, 1998, vol. 5, p. 63 Search PubMed; (c) G. J. Irvine, M. J. G. Lesley, T. B. Marder, N. C. Norman, C. R. Rice, E. G. Robins, W. R. Roper, G. R. Whittell and L. J. Wright, Chem. Rev., 1998, 98, 2685 CrossRef CAS.
  10. H. Braunschweig, B. Ganter, M. Koster and T. Wagner, Chem. Ber., 1996, 129, 1099 CrossRef CAS.
  11. H. Braunschweig and M. Müller, Chem. Ber., 1997, 130, 1295 CrossRef CAS.
  12. W. Clegg, F. J. Lawlor, T. B. Marder, P. Nguyen, N. C. Norman, A. G. Orpen, M. J. Quayle, C. R. Rice, E. G. Robins, A. J. Scott, F. E. S. Souza, G. Stringer and G. R. Whittell, J. Chem. Soc., Dalton Trans., 1998, 301 RSC.
  13. C. A. Tolman, Chem. Rev., 1977, 77, 313 CrossRef CAS.
  14. G. K. Anderson and G. J. Lumetta, Inorg. Chem., 1987, 26, 1518 CrossRef CAS.
  15. P. E. Garrou, Inorg. Chem., 1975, 14, 1435 CrossRef CAS.
  16. K. A. Azam, A. A. Frew, B. R. Lloyd, L. Manojlovic-Muir, K. W. Muir and R. J. Puddephatt, Organometallics, 1985, 4, 1400 CrossRef CAS.
  17. M. P. Brown, S. J. Cooper, A. A. Frew, L. Manojlovic-Muir, K. W. Muir, R. J. Puddephatt and M. A. Thompson, J. Chem. Soc., Dalton Trans., 1982, 299 RSC.
  18. C.-M. Che, V. W.-W. Yam, W.-T. Wong and T.-F. Lai, Inorg. Chem., 1989, 28, 2908 CrossRef CAS.
  19. R. J. Puddephatt, M. A. Thomson, L. Manojlovic-Muir, K. W. Muir, A. A. Frew and M. P. Brown, J. Chem. Soc., Chem. Commun., 1981, 805 RSC.
  20. M. P. Brown, S. J. Cooper, A. A. Frew, L. Manojlovic-Muir, K. W. Muir, R. J. Puddephatt, K. R. Seddon and M. A. Thomson, Inorg. Chem., 1981, 20, 1500 CrossRef CAS.
  21. L. Manojlovic-Muir, K. W. Muir and T. Solomun, Acta Crystallogr., Sect. B, 1979, 35, 1237 CrossRef.
  22. L. Manojlovic-Muir and K. W. Muir, J. Organomet. Chem., 1981, 219, 129 CrossRef CAS; M. P. Brown, J. R. Fisher, L. Manojlovic-Muir, K. W. Muir, R. J. Puddephatt, M. A. Thomson and K. R. Seddon, J. Chem. Soc., Chem. Commun., 1979, 931 RSC.
  23. L. Manojlovic-Muir and K. W. Muir, J. Chem. Soc., Chem. Commun., 1982, 1155 RSC.
  24. S. A. Westcott, N. J. Taylor, T. B. Marder, R. T. Baker, J. C. Calabrese and R. L. Harlow, manuscript in preparation.
  25. (a) P. Nguyen, C. Dai, N. J. Taylor, W. P. Power, T. B. Marder, N. L. Pickett and N. C. Norman, Inorg. Chem., 1995, 34, 4290 CrossRef CAS; (b) W. Clegg, C. Dai, F. J. Lawlor, T. B. Marder, P. Nguyen, N. C. Norman, N. L. Pickett, W. P. Power and A. J. Scott, J. Chem. Soc., Dalton Trans., 1997, 839 RSC.
  26. P. A. Chaloner and G. T. L. Broadsword-Strong, J. Chem. Soc., Dalton Trans., 1996, 1039 RSC.
  27. P. S. Pregosin and S. N. Sze, Helv. Chim. Acta., 1977, 60, 1371 CAS.
  28. M. Camalli, F. Caruso, S. Chaloupka, E. M. Leber, H. Rimml and L. M. Venanzi, Helv. Chim. Acta, 1990, 73, 2263 CrossRef CAS.
  29. 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., 1998, 37, 5282 CrossRef CAS.
  30. H. Nöth and W. Meister, Z. Naturforsch., Teil B, 1962, 17, 714 Search PubMed.
  31. SMART (control) and SAINT (integration) software, Siemens Analytical X-ray Instruments Inc., Madison, WI, 1994; G. M. Sheldrick, SHELXTL, version 5, Siemens Analytical X-ray Instruments Inc., Madison, WI, 1995.
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