Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis and Characterization of Air Stable σ-Bonded ortho-carborane Manganese Metal Complexes $1-[Mn(CO)_5]-2-R-1,2-closo-(σ-C_2B_{10}H_{10}$ and Their Conversion to the Stable ortho-carborane Substituted Fischer-type Carbene Compexes 1-[(CO

  • Published : 1995.07.20
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Abstract

The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

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References

  1. J. Am. Chem. Soc. v.92 Owen D. A.;Hawthorne, M. F.
  2. J. Am. Chem. Soc. v.93 Owen D. A.;Hawthorne, M. F.
  3. J. Am. Chem. Soc. v.93 Owen D. A.;Smart, J. C.;Garrett, P. M.;Hawthorne, M. F.
  4. J. Chem. Soc. Chem. Commun. Sresadola, S.;Rigo, P.;Turco, A.
  5. J. Am. Chem. Soc. v.91 Smart, J. C.;Garrett, P. M.;Hawthorne, M. F.
  6. Bull. Kor. Chem. Soc. Kim, S. J.;Kang, C. H.;Kang, S. O.
  7. J. Am. Chem. Soc. v.91 Garrett, P. M.;Smart, J. C.;Hawthorne, M. F.
  8. Inorg. Chem. v.2 Heying, T. L.;Ager, Jr., J. W.;Clark, S. L.;Alxender, R. P.;Papetti, S.;Reid, J. A.;Trotz, S. I.
  9. Organometallic Syntheses v.1 King, R. B.(Ed.)
  10. teXan: Crystal structure Analysis Package Molecular Structure Coporation
  11. J. Appl. Cryst. v.72 Burla, M. C.;Camalli, M.;Cascarano, G.;Giacovazzo, C.;Polidori, G.;Spagna, R.;Viterbo, D.
  12. ORTEP: A Fotran Thermal Ellipsolid Plot Program for Crystal Structure Illustrations Johnson, C. K.
  13. Angew. Chem., Int. Ed. Engl. v.3 Fischer, E. O.;Maasbol, a.
  14. Chem. Ber. v.100 Fischer, E. O.;Maasbol, A.
  15. J. Organomet. Chem. v.16 Fischer, E. O.;Heckl, B.;Dotz, K. H.;Muller, J.
  16. Inorg. Chem. v.8 Edgell, W. F.;Fisher, J. W.;Asato, G.;Risen, Jr., W. M.
  17. Inorg. Synth. v.10 Hawthorne, M. F.;Andrews, T. D.;Garrett, P. M.;Reintjes, M.;Tebbe, F. N.;Warren, Jr., L. F.;Wegner, P. A.;Young, D. C.
  18. Perspectives in structural Chemistry v.Ⅲ Churchill, M. R.
  19. J. Organomet. Chem. v.99 Redhouse, A. D.
  20. J. Chem. Soc. A Mills, O. S.;Redhouse, A. D.
  21. Acta Crystallogr. sec. B v.B27 Hadicke, E.;Hoppe, W.
  22. Chem. Ber. v.116 Malisch, W.;Blau, H.;Schubert, U.
  23. Organometallics v.1 Schubert, U.
  24. Z. Naturforsch., B: Anorg. Chem. Org. Chem. v.36B Fischer, E. O.;Klein, W.;Schambeck, W.;Schubert, U.
  25. Transition metal Carbene Complexes Dotz, K.H.
  26. Solid State Structures of Carbene Complexes Schubert, U.