Synthesis and X-Ray Structural Studies of Amino Acids Half Sandwich Complexes of Osmium(II)

The amino acids complexes of osmium(II), i.e. [Os(h 6-p-cymene)(h1-N-(rac)-phenylglycine methyl ester)Cl2] (A) and [Os(h 6-p-cymene) (h1-N,N'-(S)-phenylalanine amido) Cl] (B), were prepared by an ultrasound energy-assisted method at room temperature. The solid structures of the newly synthesized complexes were determined by single crystal X-ray analysis. In A, osmium is bonded to 2 chloride ligands, the h 6-coordinated p-cymene molecule, and to a nitrogen atom of the corresponding amino acid derived ligand, whereas in the case of B the central osmium is surrounded by an N, N' bidentate amino amide ligand, by an h 6-coordinated p-cymene molecule, and a chloride ligand. Both complexes have a pseudo-tetrahedral geometry. As shown by X-ray structure, A exhibited racemization of the corresponding ligand. The ligand retained its configuration in B with co-crystallization of the 2 diastereomers, ROsSC and SOsSC, in a single crystal.

Synthesis and X-Ray Structural Studies of Amino Acids Half Sandwich Complexes of Osmium(II)

The amino acids complexes of osmium(II), i.e. [Os(h 6-p-cymene)(h1-N-(rac)-phenylglycine methyl ester)Cl2] (A) and [Os(h 6-p-cymene) (h1-N,N'-(S)-phenylalanine amido) Cl] (B), were prepared by an ultrasound energy-assisted method at room temperature. The solid structures of the newly synthesized complexes were determined by single crystal X-ray analysis. In A, osmium is bonded to 2 chloride ligands, the h 6-coordinated p-cymene molecule, and to a nitrogen atom of the corresponding amino acid derived ligand, whereas in the case of B the central osmium is surrounded by an N, N' bidentate amino amide ligand, by an h 6-coordinated p-cymene molecule, and a chloride ligand. Both complexes have a pseudo-tetrahedral geometry. As shown by X-ray structure, A exhibited racemization of the corresponding ligand. The ligand retained its configuration in B with co-crystallization of the 2 diastereomers, ROsSC and SOsSC, in a single crystal.

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  • P. McMorn and G. J. Hutchings, Chem. Soc. Rev. 33, 108-22 (2004).
  • J. J. Becker and M. R. Gagn´
  • e, Acc. Chem. Res. 37, 798-804 (2004).
  • M. T. Reetz, Proc. Natl. Acad. Sci. U. S. A. 101, 5716-22 (2004).
  • B. Breit, Angew. Chem., Int. Ed. 44, 6816-25 (2005).
  • O. No vako va, J. Kasparko va, O. Vrana, P. M. van Vliet, J.Reedijk and V. Brabec, Biochemistry 34, 12369-78 (1995).
  • M. J. Bloemink, H. Engelking, S. Karentzopoulos, B. Krebs and J. Reedijk, Inorg. Chem. 35, 619-27 (1996).
  • A. H. Velders, H. Kooijman, A. L. Spek, J. G. Haasnoot, D. De Vos and J. Reedijk, Inorg. Chem. 39, 2966-67 (2000).
  • K. Severin, R. Bergs and W. Beck, Angew. Chem. Int. Ed. 37, 1634-54 (1998).
  • R. Kr¨amer, M. Maurus, K. Polborn, K. S¨unkel, C. Ro bl and W. Beck, Chem. Eur. J. 2, 1518-25 (1996).
  • R. Fish and G. Jaouen, Organometallics 22, 2166-77 (2003).
  • (a) F. Jo´oand E. Tr´ocs´anyi, J. Organomet. Chem. 231, 63-72 (1982). (b) D.A. Laidler and D.J. Molner, J. Organomet. Chem. 270, 121-29 (1984). (c) M. Nakagawa and H. Nakao, K. Watanabe, Chem. Lett. 58, 391-400 (1985). (d) S. Colonna, A. Manfredi, M. Spadoni, L. Casella and M. Gullotti, J. Chem. Soc., Perkin Trans., 71-77 (1987). (e) A. Saito h, K. Achiwa, K. Tanaka and T. Mo rimo to , J. Org. Chem. 65, 4227-35 (2000).
  • (a) A. Mori, H. Ohno, H. Nitta, K. Tanaka and S. Inoue, Synlett., 563-64 (1991). (b) M.I. Burguete, M. Collado, J. Escorihuela, F. Galindo, E. Garcı’a-Verdugo, S.V. Luis and M.J. Vicent, Tetrahedron Lett. 44, 6891-97 (2003). (c) A.V. Malkov, J.B. Hand and P. Ko`eovsk´y, Chem. Commun. 1948-49 (2003).
  • (a) A. McClarin, L.A. Dressel and J.I. Legg, J. Am. Chem. Soc. 98, 4150-54 (1976).
  • (b) P. Norman and D.A. Phipps, Inorg. Chim. Acta. 17, L19–L20. (1976). (c) Y. Ilan, Inorg. Chem. 26, 2454-61 (1987).
  • SAINT: SAX, Siemens Analytical Instruments Inc., Madison, WI, USA.
  • G. Sheldrick, SADABS: Siemens Area Detector Absorption Correction Software, University of Goettingen, Germany (1996).
  • G. Sheldrick, SHELXL97. Program for Structure ReŞnement, University of Goettingen, Germany (1997).
  • R. Kr¨amer, M. Maurus, R. Bergs, K. Polborn, K. S¨unkel, B. Wagner and W. Beck, Chem. Ber. 126, 1969-76 (1993).
  • H. Brunner, T. Neuhierl and B. Nuber, , Eur. J. Inorg. Chem. 1877-81 (1998).
  • J.L. Farrugia, J. Appl. Crystallogr. 32, 837-44 (1999).
  • (a) J.W. Faller and A.R. Lavoie, Orgnometallics 20, 7562-67 (2001).
  • (b) H.Y. Rhyoo, H.J. Park and Y.K. Chung, Chem. Commun. 2064-65 (2001). (c) H.Y. Rhyoo, Y.A. Yoon, H.J. Park and Y.K. Chung, Tetrahedron Lett. 42, 5045-51 (2001). (d) H.Y. Rhyoo, H.J. Park, W.H. Suh and Y.K. Chung, Tetrahedron Lett. 43, 269-76 (2002).
  • (a) I.M. Pastor, P. V¨astil¨a and A. Adolfsson, Chem. Commun. 2046-47 (2002). (b) I.M. Pastor, P. V¨astil¨a and A. Adolfsson, Chem. Eur. J. 9, 4031-40 (2003). (c) A. Bİgevig, I.M. Pastor and A. Adolfsson, Chem. Eur. J. 10, 294-99 (2004). (a) T. Ohta, S. Nakahara, Y. Shigemura, K. Hattori and I. Furukawa, Chem. Lett. 6, 491-92 (1998). (b) T. Ohta, S. Nakahara, Y. Shigemura, K. Hattori and I. Furukawa, Appl.
  • Organomet. Chem. 15, 699-707 (2001).
  • (c) D.Carmona, F.J.Lahoz, R. Atencio, L.A. Oro, M.P. Lamata, F. Viguri, E.S. Jos´e, C. Vega, J. Reyes, F. Jo´o
  • and A. Kath´o, Chem. Eur. J. 5, 1544-52 (1999).
  • (d) A. Kath´o , D. Carmo na, F. Viguri, C.D. Remacha, J. Ko v´acs, F. Jo´oand L.A. Oro, J. Organomet. Chem. 593, 299-307 (2000).
  • (a) H. Brunner and M. Weber, M. Zabel, Coord. Chem. Rew. 242, 3-32 (2003). (b) H. Brunner, M. Weber, M. Zabel and T. Zwack, Angew. Chem. Int. Ed. 42, 1859-68 (2003).
  • M.A. Bennett, T.N. Huang, T.W. Manheson and A.K. Smith, Fnorg. Synth. 21, 74-80 (1982).