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DOI: 10.1039/A905464B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3413-3417

The synthesis and molecular structures of the crystalline 1-aza-2-phospha(V)allyllithium compounds [Li(LL[hair space]′[hair space])(OEt2)2] and [Li(LL[hair space]′[hair space])]2 [LL[hair space]′ = CH(SiMe3)P(Ph)2[double bond, length half m-dash]NSiMe3] and the preparation and characterisation of the new phosphinimines CH(R1)(R2)P(Ph)2[double bond, length half m-dash] NSiMe3 [R1 = R2 = SiMe3; R1 = H, R2 = Si(Me)2NEt2][hair space]†

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Peter B. Hitchcock, Michael F. Lappert, Patrick G. H. Uiterweerd and Zhong-Xia Wang

Abstract

Reaction of CH2(SiMe3)P(Ph)2[double bond, length half m-dash]NSiMe3 (HLL[hair space]′) I with LiBun afforded, after recrystallisation from diethyl ether, [Li{CH(SiMe3)P(Ph)2[double bond, length half m-dash]NSiMe3}(OEt2)2]. Removal of the co-ordinating Et2O molecules in vacuo and subsequent recrystallisation from hexane yielded the solvent-free dimeric lithium complex [Li{CH(SiMe3)P(Ph)2[double bond, length half m-dash]NSiMe3}]2. The crystal structures of the crystalline compounds [Li(LL[hair space]′)(OEt2)2] and the fused dinuclear [Li(LL[hair space]′)]2 are reported. Each contains a planar Li(LL[hair space]′) ring. The Li(2)–N bond of the Li(LL[hair space]′) moiety of the latter is also part of a six-membered Li(2)–N–Li(1)–N–P–C ring, planar except for Li(2); the two Li atoms are bridged by a second [LL[hair space]′]– ligand, so that the bridgehead lithium atom Li(2) is bound to the allyl carbon of each [LL[hair space]′]– ligand, whereas Li(1) is bound to two nitrogen atoms. In toluene-d8, this compound shows singlet 7Li-{1H} and 31P-{1H} NMR spectral signals, even at low temperatures. Its reaction with Me3SiO3SCF3 afforded the phosphinimine CH(SiMe3)2P(Ph)2[double bond, length half m-dash] NSiMe3 (HLL″) II, a potential precursor for a new 1-aza-2-phospha(V)allyl ligand, as was shown by its straightforward lithiation to yield Li(LL″). The novel phosphinimine CH2{SiMe2(NEt2)}P(Ph)2[double bond, length half m-dash]NSiMe3 (HLL‴) III was synthesized by reaction of Li[CH2P(Ph)2[double bond, length half m-dash]NSiMe3] with Et2NSi(Me)2Cl and, similar to the lithiation of II, reaction of III with LiBun afforded Li(LL‴) in high yield.

References

  1. F. López-Ortiz, E. Peláez-Arango, B. Tejerina, E. Pérez-Carreño and S. García-Granda, J. Am. Chem. Soc., 1995, 117, 9972 Search PubMed.
  2. A. Müller, B. Neumüller and K. Dehnicke, Chem. Ber., 1996, 129, 253 Search PubMed.
  3. (a) A. Müller, B. Neumüller and K. Dehnicke, Angew. Chem., Int. Ed. Engl., 1997, 36, 2350 Search PubMed; (b) A. Müller, M. Krieger, B. Neumüller, K. Dehnicke and J. Magull, Z. Anorg. Allg. Chem., 1997, 623, 1081 Search PubMed.
  4. J. C. Wilburn and R. H. Neilson, Inorg. Chem., 1979, 18, 347 Search PubMed.
  5. P. B. Hitchcock, M. F. Lappert and Z.-X. Wang, Chem. Commun., 1997, 1113 Search PubMed.
  6. P. B. Hitchcock, M. F. Lappert and Z.-X. Wang, J. Chem. Soc., Dalton Trans., 1997, 1953 Search PubMed.
  7. H. Schmidbaur and G. Jonas, Chem. Ber., 1967, 100, 1120 Search PubMed.
  8. C. H. Yoder, D. R. Griffith and C. D. Schaeffer, Jr., J. Inorg. Nucl. Chem., 1970, 32, 3689 Search PubMed; S. S. Washburne and W. R. Peterson, J. Organomet. Chem., 1970, 21, 59 Search PubMed.
  9. K. Itoh, M. Okamura and Y. Ishii, J. Organomet. Chem., 1974, 65, 327 Search PubMed.
  10. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  11. C. M. Ong and D. W. Stephan, J. Am. Chem. Soc., 1999, 121, 2939 Search PubMed; A. Kasani, R. P. Kamalesh Babu, R. McDonald and R. G. Cavell, Angew. Chem., Int. Ed., 1999, 38, 1483 Search PubMed.
  12. H. R. Allcock, Chem. Rev., 1972, 72, 315 Search PubMed.
  13. J. Emsley and D. Hall, The Chemistry of Phosphorus, Harper & Row, London, 1976 Search PubMed.
  14. A. Recknagel, A. Steiner, M. Noltemeyer, S. Brooker, D. Stalke and F. T. Edelmann, J. Organomet. Chem., 1991, 414, 327 Search PubMed; A. Steiner and D. Stalke, Inorg. Chem., 1993, 32, 1977 Search PubMed.
  15. P. Imhoff, S. C. A. Nefkens, C. J. Elsevier, K. Goubitz and C. H. Stam, Organometallics, 1991, 10, 1421 Search PubMed.
  16. H. R. Allcock, W. D. Coggio, M. Parvez and M. L. Turner, Organometallics, 1991, 10, 677 Search PubMed.
  17. A. Bondi, J. Phys. Chem., 1964, 68, 441 Search PubMed.
  18. R. A. Jones, A. L. Stuart and T. C. Wright, J. Am. Chem. Soc., 1983, 105, 7459 Search PubMed; H. H. Karsch, K. Zellner and G. Müller, Organometallics, 1991, 10, 2884 Search PubMed; E. Hey-Hawkins and E. Sattler, J. Chem. Soc., Chem. Commun., 1992, 775 Search PubMed; A. Pape, M. Lutz and G. Müller, Angew. Chem., Int. Ed. Engl., 1994, 33, 2281 Search PubMed.
  19. A. Müller, B. Neumüller, K. Dehnicke, J. Magull and D. Fenske, Z. Anorg. Allg. Chem., 1997, 623, 1306 Search PubMed.
  20. P. Imhoff and C. J. Elsevier, J. Organomet. Chem., 1989, 361, C61 Search PubMed; P. Imhoff, J. H. Gülpen, K. Vrieze, W. J. J. Smeets, A. L. Spek and C. J. Elsevier, Inorg. Chim. Acta, 1995, 235, 77 Search PubMed; P. Imhoff, R. van Asselt, J. M. Ernsting, K. Vrieze, C. J. Elsevier, W. J. J. Smeets, A. L. Spek and A. P. M. Kentgens, Organometallics, 1993, 12, 1523 Search PubMed; M. W. Avis, K. Vrieze, H. Kooijman, N. Veldman, A. L. Spek and C. J. Elsevier, Inorg. Chem., 1995, 34, 4092 Search PubMed; M. W. Avis, K. Vrieze, J. M. Ernsting, C. J. Elsevier, N. Veldman, A. L. Spek, K. V. Katti and C. L. Barnes, Organometallics, 1996, 15, 2376 Search PubMed.
  21. D. Barr, W. Clegg, R. E. Mulvey and R. Snaith, J. Chem. Soc., Chem. Commun., 1984, 79 Search PubMed.
  22. R. D. Rogers, J. L. Atwood and R. Grüning, J. Organomet. Chem., 1978, 157, 229 Search PubMed; D. Barr, W. Clegg, R. E. Mulvey and R. Snaith, J. Chem. Soc., Chem. Commun., 1984, 285 Search PubMed.
  23. C. Eaborn, Z.-R. Lu, P. B. Hitchcock and J. D. Smith, Organometallics, 1996, 15, 1651 Search PubMed.
  24. G. M. Sheldrick, SHELXS 86, a package for the solution of crystal structures, University of Göttingen, 1986.
  25. G. M. Sheldrick, SHELXL 93, a package for crystal structure refinement, University of Göttingen, 1993.
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