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DOI: 10.1039/A608473G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2713-2724

Stereoselective synthesis of chiral multidentate ligands with As2NP or As4P donor atoms[hair space]*

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Roy J. Doyle, Geoffrey Salem and Anthony C. Willis

Abstract

The asymmetric bidentate ligand (±)-(2-aminophenyl)(2-chlorophenyl)methylphosphine has been prepared via chemoselective cleavage of the phenyl group from (±)-(2-aminophenyl)methylphenylphosphine using lithium in tetrahydrofuran (thf), to give (2-aminophenyl)methylphosphine upon hydrolysis, followed by deprotonation of the secondary phosphine with sodium in thf and subsequent reaction with 1,2-dichlorobenzene. The chlorophenyl-substituted tertiary phosphine has been resolved by the method of metal complexation. The absolute configuration of the R enantiomer of the ligand has been assigned by a crystal structure determination of the diastereomeric palladium(II) complex [(SP),(R)]-[(2-aminophenyl)(2- chlorophenyl)methylphosphine-N,P]{1-[1- (dimethylamino)ethyl]naphthyl-C2,N} palladium(II) hexafluorophosphate. Reaction of (±)-(2-aminophenyl)(2-chlorophenyl)methylphosphine with an equimolar quantity of sodium (2-dimethylarsinophenyl)methylarsenide in thf at -20 ± 5 °C gave a 1[hair space]:[hair space]1 diastereomeric mixture of the chiral pentadentate ligands (RAs*,RAs*,SP *)-(±)- and (RAs*,SAs*,SP *)-(±)-{2-[(2-dimethylarsinophenyl) methylarsinophenyl}{2-[(2-dimethylarsinophenyl) methylarsinoamino]phenyl}methylphosphine. The chiral quadridentate ligand (RAs*,SP*)-(±)-1-[(2- aminophenyl)methylphosphino]-2-[(2-dimethylarsinophenyl)methylarsino] benzene can be isolated, however, when the coupling reaction is performed at 50 ± 5 °C. The chiral multidentate ligands have been isolated by complexation to cobalt(III) and the structures of the three complexes determined by X-ray analyses. It is clear from the structural data that the quadridentate ligand has formed a single dichlorocobalt(III) complex with cis-α stereochemistry and in which the stereogenic arsenic and phosphorus atoms of the ligand have opposite relative configurations. Two other complexes have also been isolated from the coupling reaction: trans-dichlorobis[1,2-phenylenebis(dimethylarsine)]cobalt( III) chloride and bis[(2-aminophenyl)methylphenylphosphine]dichlorocobalt(III) chloride. The latter is isolated as an isomeric mixture. The formation of asymmetric bidentate (±)-(2-aminophenyl)methylphenylphosphine is believed to result from reduction of the chloro group in the tertiary phosphine precursor by the sodium arsenide reagent. Metal-assisted methylation of a (2-dimethylarsinophenyl)methylarsino moiety by methanol is postulated to account for the formation of 1,2-phenylenebis(dimethylarsine) in the reaction. Optically active analogues of the three multidentate ligands have also been synthesized by reaction of (R)-(2-aminophenyl)(2-chlorophenyl)methylphosphine with sodium (2-dimethylarsinophenyl)methylarsenide in thf and similarly isolated by complexation to cobalt(III).

References

  1. See, for example, (a) T.-S. Chou, C.-H. Tsao and S. C. Hung, J. Organomet. Chem., 1986, 312, 53 CrossRef CAS; (b) P. Brooks, M. J. Gallagher and A. Sarroff, Aust. J. Chem., 1987, 40, 1341 CAS; (c) O. Walter, T. Klein, G. Huttner and L. Zsolnai, J. Organomet. Chem., 1993, 458, 63 CrossRef CAS; (d) J. Leitch, G. Salem and D. C. R. Hockless, J. Chem. Soc., Dalton Trans., 1995, 649 RSC; (e) K. Burgess, M. J. Ohlmeyer and K. H. Whitmire, Organometallics, 1992, 11, 3588 CrossRef CAS; (f) N. Gabbitas, G. Salem, M. Sterns and A. C. Willis, J. Chem. Soc., Dalton Trans., 1993, 3271 RSC; (g) A. A. Danopoulos, P. G. Edwards, M. Harman, M. B. Hursthouse and J. S. Parry, J. Chem. Soc., Dalton Trans., 1994, 977 RSC; (h) R. J. Doyle, G. Salem and A. C. Willis, J. Chem. Soc., Dalton Trans., 1995, 1867 RSC.
  2. C. E. Barclay, G. Deeble, R. J. Doyle, S. A. Elix, G. Salem, T. L. Jones, S. B. Wild and A. C. Willis, J. Chem. Soc., Dalton Trans., 1995, 57 RSC.
  3. C. W. G. Ansell, M. K. Cooper, K. P. Dancey, P. A. Duckworth, K. Henrick, M. McPartlin, G. Organ and P. A. Tasker, J. Chem. Soc., Chem. Commun., 1985, 437 RSC.
  4. T. R. Carlton and C. D. Cook, Inorg. Chem., 1971, 10, 2628 CrossRef CAS.
  5. C. W. G. Ansell, M. K. Cooper, K. P. Dancey, P. A. Duckworth, K. Henrick, M. McPartlin and P. A. Tasker, J. Chem. Soc., Chem. Commun., 1985, 439 RSC.
  6. R. B. King and P. N. Kapoor, J. Am. Chem. Soc., 1971, 93, 4158 CrossRef.
  7. B. Bosnich, S. T. D. Lo and E. A. Sullivan, Inorg. Chem., 1975, 14, 2305 CrossRef CAS.
  8. B. Bosnich, W. G. Jackson and S. B. Wild, J. Am. Chem. Soc., 1973, 95, 8269 CrossRef CAS.
  9. M. Atoh, K. Kashiwabara and J. Fujita, Bull. Chem. Soc., Jpn., 1986, 59, 1001 CAS.
  10. A. L. Airey, G. F. Swiegers, S. B. Wild and A. C. Willis, J. Chem. Soc., Chem. Commun., 1995, 693 RSC.
  11. A. L. Airey, G. F. Swiegers, S. B. Wild and A. C. Willis, J. Chem. Soc., Chem. Commun., 1995, 695 RSC.
  12. R. J. Doyle, G. Salem and A. C. Willis, J. Chem. Soc., Chem. Commun., 1994, 1587 RSC.
  13. D. G. Allen, G. M. McLaughlin, G. B. Robertson, W. L. Steffen, G. Salem and S. B. Wild, Inorg. Chem., 1982, 21, 1007 CrossRef CAS.
  14. N. K. Roberts and S. B. Wild, J. Am. Chem. Soc., 1979, 101, 6254 CrossRef CAS.
  15. R. S. Nyholm, J. Chem. Soc., 1950, 2071 RSC.
  16. B. Bosnich, W. G. Jackson and J. W. McLaren, Inorg. Chem., 1974, 13, 1133 CrossRef CAS.
  17. PATTY, P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. Garcia-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla, DIRDIF program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1992.
  18. DIRDIF 92, P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. Garcia-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla, DIRDIF program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1992.
  19. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, Table 2.2 A Search PubMed.
  20. J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 781 CrossRef.
  21. D. C. CreaghW. J. McAuley, International Tables for Crystallography, ed. A. J. C. Wilson, Kluwer Academic Publishers, Boston, 1992, vol. C, Table 4.2.6.8, pp. 219-222 Search PubMed.
  22. D. C. Creagh and J. H. Hubbell, International Tables for Crys-tallography, ed. A. J. C. Wilson, Kluwer Academic Publishers, Boston, 1992, vol. C, Table 4.2.4.3, pp. 200–206 Search PubMed.
  23. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TX, 1985 and 1992.
  24. M. K. Cooper and J. M. Downes, Inorg. Chem., 1978, 17, 880 CrossRef CAS.
  25. R. S. Cahn, C. K. Ingold and V. Prelog, Angew. Chem., Int. Ed. Engl., 1966, 5, 385 CrossRef CAS.
  26. See, for example, K. M. Flynn, B. D. Murray, M. M. Olmstead and P. P. Power, J. Am. Chem. Soc., 1983, 105, 7460 Search PubMed; G. Suss-Fink, K. M. Heberhold, W. Buhlmeyer, A. Gieren and T. Hubner, J. Organomet. Chem., 1987, 321, 37 CrossRef CAS; T. Chivers, K. S. Dhathathreyan, C. Lensink and J. F. Richardson, Inorg. Chem., 1988, 27, 1570 CrossRef; A. J. Arduengo III, M. Lattman, H. V. R. Dias, J. C. Calabrese and M. Kline, J. Am. Chem. Soc., 1991, 113, 1799 CrossRef CAS; A. Strube, G. Huttner and L. Zsolnai, J. Organomet. Chem., 1990, 399, 255 CrossRef.
  27. I. Kinoshita, Y. Yokato, K. Matsumoto, S. Ooi, K. Kashiwabara and J. Fujita, Bull. Chem. Soc. Jpn., 1983, 56, 1067 CAS; M. Kita, K. Kashiwabara, I. Kinoshita, J. Fujita, H. Tanaka and S. Ohba, Bull. Chem. Soc. Jpn., 1994, 67, 2457 CAS.
  28. D. Forster, Adv. Organomet. Chem., 1979, 17, 255 CAS.
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