View PDF Version
 
DOI: 10.1039/A904742E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 4103-4110

Dimolybdenum(II) complexes linked by axial cyano bridges to organic and organometallic ligands: syntheses, structures, and characterization[hair space]†

(Note: The full text of this document is currently only available in the PDF Version )

Wen-Mei Xue, Fritz E. Kühn, Guofang Zhang, Eberhardt Herdtweck and Gabriele Raudaschl-Sieber

Abstract

Reaction of trans-[Mo2(µ-OAc)2(dppma)2(NCCH3)n][BF4]2 (n = 0–2, dppma = bis(diphenylphosphino)methylamine) with a variety of ligands containing a nitrile group leads to axially substituted complexes of formula trans-[Mo2(µ-OAc)2(dppma)2(RCN)2][BF4]n (n = 0, 2), R can be both an organic and an organometallic moiety. The obtained complexes are characterized by 1H-, 13C-, and 31P{1H}-NMR, IR, Raman, and UV/Vis spectroscopy, elemental analyses and cyclic voltammetry. Four of these complexes are additionally examined by single crystal X-ray analysis. The applied methods show that the axial ligands influence the spectroscopic and crystallographic data of the central moiety only slightly. However, while X-ray crystallography shows the MoMo quadruple bond length not to be significantly influenced by axial ligands, Raman spectroscopy gives a more detailed insight: organic ligands of the type NCR (R = CH3, t-Bu, C6H5etc.) in axial positions weaken the MoMo interaction less than organometallic ligands of the type [NC–M(CO)5]– (M = Cr, Mo, W) and NCFe(CO)2Cp. UV/Vis examination indicates charge transfer from the organometallic axial ligands to the MoMo moiety.

References

  1. F. A. Cotton and R. A. Walton, Multiple Bonds between Metal Atoms, 2nd edn., Oxford University Press, London, 1993 and references cited therein Search PubMed.
  2. M. Bakir and R. A. Walton, Polyhedron, 1988, 7, 1279 CrossRef CAS.
  3. (a) L. J. Farrugia, A. McVitie and R. D. Peacock, Inorg. Chem., 1988, 27, 1257 CrossRef CAS; (b) F. A. Cotton, J. Eglin and K. J. Wiesinger, Inorg. Chim. Acta, 1992, 195, 11 CrossRef CAS; (c) D. I. Arnold, F. A. Cotton and F. E. Kühn, Inorg. Chem., 1996, 35, 4733 CrossRef CAS; (d) F. A. Cotton, F. E. Kühn and A. Yokochi, Inorg. Chim. Acta, 1996, 252, 251 CrossRef CAS; (e) Y. Y. Wu, J. D. Chen, L. S. Liou and J. C. Wang, Inorg. Chim. Acta, 1997, 258, 193 CrossRef CAS; (f) D. I. Arnold, F. A. Cotton and F. E. Kühn, Inorg. Chem., 1996, 35, 5764 CrossRef CAS; (g) F. A. Cotton and F. E. Kühn, Inorg. Chim. Acta, 1996, 252, 257 CrossRef CAS.
  4. F. E. Kühn, I. S. Gonçalves, A. D. Lopes, J. P. Lopes, C. C. Romão, W. Wachter, J. Mink, L. Hajba, J. A. Parola, F. Pina and J. Sotomayor, Eur. J. Inorg. Chem., 1999, 295 CrossRef CAS.
  5. (a) F. A. Cotton and K. Wiesinger, Inorg. Chem., 1991, 30, 871 CrossRef CAS; (b) F. A. Cotton and K. Wiesinger, Inorg. Synth., 1992, 29, 134 CAS; (c) F. A. Cotton and F. E. Kühn, J. Am. Chem. Soc., 1996, 118, 5826 CrossRef CAS; (d) F. A. Cotton, C. A. Murillo, L. Daniels and X. Wang, Polyhedron, 1998, 17, 2781 CrossRef CAS; (e) G. Pimblett, C. D. Garner and W. Clegg, J. Chem. Soc., Dalton Trans., 1986, 1257 RSC.
  6. (a) R. B. King, Inorg. Chem., 1967, 6, 25 CrossRef CAS; (b) J. K. Ruff, Inorg. Chem., 1968, 7, 1821 CrossRef CAS.
  7. P. M. Treichel and D. C. Molzahn, Synth. React. Inorg. Met.-Org. Chem., 1979, 9, 21 CAS.
  8. S. Takahashi, Y. Kuroyama, K. Sonogashira and N. Hagihara, Synthesis, 1980, 627 CrossRef CAS.
  9. (a) Z. Otwinowski and W. Minor, Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology, ed. W. C. Carter and R. M. Sweet, Jr., Academic Press, USA, 1996, 276 Search PubMed; (b) International Tables for Crystallography, Vol. C, Tables 6.1.1.4 (pp. 500–502), 4.2.6.8 (pp. 219–222) and 4.2.4.2 (pp. 193–199), Ed. A. J. C. Wilson, Kluwer Academic Publishers, Dordrecht, 1992 Search PubMed; (c) G. Artus, W. Scherer, T. Priermeier and E. Herdtweck, ‘STRUX-V’, A Program System to Handle X-Ray Data, TU München, 1997; (d) A. L. Spek, PLATON, A Multipurpose Crystallographic Tool, Utrecht University, 1999; (e) A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori and M. Camalli, SIR92, J. Appl. Cryst., 1994, 27, 435 CrossRef; (f) G. M. Sheldrick, SHELXL-97, University of Göttingen, 1998.
  10. (a) J. M. Mayer and E. H. Abbott, Inorg. Chem., 1983, 22, 2774 CrossRef CAS; (b) F. A. Cotton and K. J. Wiesinger, Inorg. Chem., 1991, 30, 871 CrossRef CAS.
  11. A. Carvill, P. Higgins, M. McCann, H. Ryan and A. Shiels, J. Chem. Soc., Dalton Trans., 1989, 2435 RSC.
  12. A. Das, J. C. Jeffery, J. P. Maher, J. A. McCleverty, E. Schatz, M. D. Ward and G. Wollermann, Inorg. Chem., 1993, 32, 2145 CrossRef CAS.
  13. P. Vella and J. Zubieta, J. Inorg. Nucl. Chem., 1978, 40, 477 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.