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Nucleophilic addition of methanol to nitrosodicyanomethanide in the coordination sphere of MII ions (M = Ni, Cu, Co and Pd); nitrosodicyanomethanide as an O-coordinating ligand for nickel(II)

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Abstract

The systems MII-ONC(CN)2 −-L-MeOH-H2O [M = Ni, Cu, Co or Pd; L = pyrazole (pz)] were studied to determine conditions for the nucleophilic addition of MeOH to nitrosodicyanomethanide (ndcm)− in the metal coordination sphere. Compounds containing two or three bidentate anionic chelate ligands derived from methyl-2-cyano-2-(hydroxyimino)ethanimidic acid, H(mcoe), formed by nucleophilic addition of MeOH to ONC(CN)2 −, were isolated: [Cu(mcoe)2(H2O)2] (elongated pseudo-octahedron with two water molecules at long axial distances), [Co(mcoe)3] (approximate octahedron) and [Pd(mcoe)2] (square-planar). In the CoII system, oxidation to CoIII took place. In addition, simple nitrosodicyanomethanide compounds [Ni(ndcm)2(pz)4] (nearly octahedral) and [Pd(ndcm)2(pz)2] (square-planar) were obtained. The crystal structure of trans-[Ni(ndcm)2(pz)4] has been elucidated by X-ray crystallography. The NiII atom is nearly octahedrally coordinated by four nitrogens of pz and two oxygens of (ndcm)−. This compound is the first example of a transition metal oxygen-coordinated nitrosodicyanomethanide complex with a short metal-oxygen bond. The remaining compounds were characterized by i.r. and electronic spectra.

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References

  1. F. Valach, J. Kohout, M. Dunaj-Jurčo, M. Hvastijová and J. Gažo, J. Chem. Soc., Dalton Trans., 1867 (1979); (b) M. Hvastijová, J. Kohout and J. Gažo, J. Inorg. Nucl. Chem., 43, 2337 (1981); (c) J. Kohout and M. Hvastijová, Inorg. Chim. Acta, 131, 33 (1987); (d) M. Hvastijová, J. Kohout and J. Gažo, J. Coord. Chem., 12, 27 (1982); (e) M. Hvastijová, J. Kohout, A. Adamíková and P. Fodran, J. Coord. Chem., 14, 259 (1986).

  2. M. Hvastijová, J. Kohout, J. Klimčíková and H. Köhler, J. Coord. Chem., 15, 409 (1987); J. Mroziński, J. Kohout, M. Hvastijová and H. Köhler, Transition Met. Chem., 11, 481 (1986); M. Hvastijová, J. Kohout, H. Köhler and G. Ondrejovič, Z. Anorg. Allg. Chem., 566, 111 (1988); J. Kožíšek, M. Hvastijová, J. Kohout, J. Mroziński and H. Köhler, J. Chem. Soc., Dalton Trans., 1773 (1991).

    Google Scholar 

  3. J. Kožíšek, M. Hvastijová and J. Kohout, Inorg. Chim. Acta, 168, 157 (1990).

    Google Scholar 

  4. M. Hvastijová, J. Kožíšek, J. Kohout and J. G. Díaz, Inorg. Chim. Acta, 236, 163 (1995).

    Article  Google Scholar 

  5. M. Hvastijová, J. Kožíšek, J. Kohout and L. Jäger, J. Coord. Chem., 36, 195 (1995); (b) M. Hvastijová, J. Kožíšek and J. Kohout in G. Ondrejovič and A. Sirota (eds), Current Trends in Coordination Chemistry, 15th CCC, STU Press, Bratislava 1995, p. 113.

    Google Scholar 

  6. G. Longo, Gazz. Chim., 61, 575 (1931).

    CAS  Google Scholar 

  7. Stoe & Cie, DIF4, Stoe Four-Circle Diffractometer Control Program, Version 7.08, Stoe & Cie, Darmstadt, Germany, 1991; (b) Stoe & Cie, REDU4, Stoe Four-Circle Diffractometer Reduction Program, Version 7.08, Stoe & Cie, Darmstadt, Germany, 1991.

    Google Scholar 

  8. G. M. Sheldrick, SHELX76, Program for Crystal Structure Determination, University of Cambridge, England, 1976; (b) G. M. Sheldrick, Acta Crystallogr., Sect. A, 46, 467 (1990); (c) G. M. Sheldrick, SHELXL93, Program for Crystal Structure Refinement, University of Göttingen, Germany, 1993.

    Google Scholar 

  9. B. J. Hathaway and D. E. Billing, Coord. Chem. Rev., 5, 143 (1970); B. J. Hathaway, J. Chem. Soc., Dalton Trans., 1196 (1972).

    Article  CAS  Google Scholar 

  10. J. Kožíšek, M. Hvastijová and J. Kohout, unpublished observation.

  11. A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd Edit, Elsevier, Amsterdam, 1984, (a) p. 544; (b) p. 473.

    Google Scholar 

  12. C. K. Johnson, ORTEPII. Report ORNL-3794, revised, Oak Ridge National Laboratory, TN, USA, 1971.

    Google Scholar 

  13. M. Hvastijová, J. Kožíšek, J. Kohout, J. Mroziński, L. Jäger and I. Svoboda, Polyhedron, 16, 463 (1997).

    Article  Google Scholar 

  14. A. Kolbe and H. Köhler, Z. Anorg. Allg. Chem., 373, 230 (1970); (b) H. Köhler, Koord. Khim. (Moscow), 3, 139 (1977); (c) V. V. Skopenko, Yu. L. Zub, V. F. Bolelyj and H. Köhler, Koord. Khim. (Moscow), 10, 1317 (1984).

    Article  CAS  Google Scholar 

  15. A. Zecchina, L. Cerruti, S. Coluccia and E. Borello, J. Chem. Soc. (B), 1363 (1967).

  16. R. J. H. Clark and C. S. Williams, Inorg. Chem., 4, 350 (1965); R. J. H. Clark and C. S. Williams, J. Chem. Soc. (A), 1425 (1966).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Inorganic Chemistry, Darmstadt University of Technology, D-64287, Darmstadt, Germany

    Johann W. Buchler

  2. Department of Inorganic Chemistry, Slovak Technical University, 812 37, Bratislava, Slovakia

    Mária Hvastijová, Jiří Kohout & Jozef Kožíšek

Authors
  1. Johann W. Buchler
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  2. Mária Hvastijová
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  3. Jiří Kohout
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  4. Jozef Kožíšek
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Buchler, J.W., Hvastijová, M., Kohout, J. et al. Nucleophilic addition of methanol to nitrosodicyanomethanide in the coordination sphere of MII ions (M = Ni, Cu, Co and Pd); nitrosodicyanomethanide as an O-coordinating ligand for nickel(II). Transition Metal Chemistry 23, 215–220 (1998). https://doi.org/10.1023/A:1015763506523

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