Skip to main content
SpringerLink
Log in

cis-Dioxomolybdenum(VI) complexes of sterically encumbered phenol-based tetradentate N2O2 ligands: Structural, spectroscopic, and electrochemical studies

  • Structural Science in India
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

Two cis-dioxomolybdenum(VI) complexes [MoO2L] (L: L 1, 2 and L: L 2, 3) in a phenol-based sterically encumbered N2O2 ligand environment have been synthesized, and their crystallographic characterizations are reported. The orange crystals of 2 are monoclinic, space group P21/a with unit cell dimensions as a=16.2407(17) Å, b=7.2857(8) Å, c=18.400(2) Å, β=98.002(9)°, Z=4, and d cal=1.486 g cm−3. The light orange crystals of 3, however, are orthorhombic, space group, Pbcn, with unit cell dimensions a=8.3110(12) Å, b=12.637(3) Å, c=34.673(5) Å, Z=4, and d cal=1.187 g cm−3. The structures were refined by a full-matrix least-squares procedure on F 2 to a final R=0.046 (0.055 for 3) using 4944 (3677) all independent data. In both the cases, the Mo atom exists in a distorted octahedral geometry defined by a N2O4 donor set, which features a cis-Mo(–O)2 and a trans-Mo(OPh)2 arrangement. Compound 2 undergoes a quasireversible one-electron reduction at −1.3 V vs Ag/AgCl reference due to MoVIO2/MoVO2 electron transfer and thus providing a rare example of steric solution to the comproportionation–dimerization problem encountered frequently in the development of valid biomimetic models for the active sites of oxomolybdenum enzymes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Molybdenum and Tungsten: Their roles in biological processes (2002) In: Siegel A, Siegel H (eds) Metal ions in biological systems, vol. 39. Marcel Dekker, New York

  2. Hill R (1996) Chem Rev 96:2757

    Article  Google Scholar 

  3. Enemark JH, Cooney JJA, Wang J-J, Holm RH (2004) Chem Rev 104:1175

    Article  CAS  Google Scholar 

  4. Rajagopalan KV (1991) Adv Enzymol Relat Areas Mol Biol 64:215

    Article  CAS  Google Scholar 

  5. Rajagopalan KV, Johnson JL (1992) J Biol Chem 267:10199

    CAS  Google Scholar 

  6. Hille R, Sprecher H (1987) J Biol Chem 262:10914

    CAS  Google Scholar 

  7. Holm RH (1990) Coord Chem Rev 100:183

    Article  CAS  Google Scholar 

  8. Enemark JH, Young CG (1994) Adv Inorg Chem 40:1

    Article  CAS  Google Scholar 

  9. Schultz BE, Gheller SF, Muetterties MC, Scott MJ, Holm RH (1993) J Am Chem Soc 115:2714

    Article  CAS  Google Scholar 

  10. Holm RH, Berg JM (1984) Pure Appl Chem 56:1645

    CAS  Google Scholar 

  11. Berg JM, Holm RH (1985) J Am Chem Soc 107:917

    Article  CAS  Google Scholar 

  12. Gheller SF, Schultz BE, Scott MJ, Holm RH (1992) J Am Chem Soc 114:6934

    Article  CAS  Google Scholar 

  13. Xiao Z, Young CG, Enemark JH, Wedd AG (1992) J Am Chem Soc 114:9194

    Article  CAS  Google Scholar 

  14. Xiao Z, Bruck MA, Enemark JH, Young CG, Wedd AG (1996) Inorg Chem 35:7508

    Article  CAS  Google Scholar 

  15. Dutta SK, McConville DB, Youngs WJ, Chaudhury M (1997) Inorg Chem 36:2517 and references therein

    Article  CAS  Google Scholar 

  16. Chen GJJ, McDonald JW, Newton WE (1976) Inorg Chem 15:2612

    Article  CAS  Google Scholar 

  17. Velusamy M, Palaniandavar M, Gopalan RS, Kulkarni GU (2003) Inorg Chem 42:8283

    Article  CAS  Google Scholar 

  18. Perrin DD, Armarego WLF, Perrin DR (1980) Purification of laboratory chemicals, 2nd edn. Pergamon, Oxford, England

    Google Scholar 

  19. Dutta SK, Kumar SB, Bhattacharyya S, Tiekink ERT, Chaudhury M (1997) Inorg Chem 36:4954

    Article  CAS  Google Scholar 

  20. Altomare A, Cascarano G, Giacovazzo C, Guagliardi A, Burla MC, Polidori G, Camalli N (1994) J Appl Crystallgr 27:435

    Article  Google Scholar 

  21. TeXsan Software for single-crystal structure analysis (1997) version 1.7; Molecular Structure Corporation: 3200A Research Forest Drive, The Woodlands, TX 77381

  22. Cotton FA, Wing RM (1965) Inorg Chem 4:867

    Article  CAS  Google Scholar 

  23. Tatsumi K, Hoffman R (1980) Inorg Chem 19:2656

    Article  CAS  Google Scholar 

  24. Stiefel EI (1977) Prog Inorg Chem 22:1

    Article  CAS  Google Scholar 

  25. Subramanian P, Spence JT, Ortega R, Enemark JH (1984) Inorg Chem 23:2564

    Article  CAS  Google Scholar 

  26. Dowerah D, Spence JT, Singh R, Wedd AG, Wilson GL, Farchione F, Enemark JH, Kristofzski J, Bruck M (1987) J Am Chem Soc 109:5655

    Article  Google Scholar 

  27. Rajan OA, Spence JT, Lemen C, Minelli M, Sato M, Enemark JH, Kroneck PHM, Sulger K (1983) Inorg Chem 22:3065

    Article  CAS  Google Scholar 

  28. Topich J (1981) Inorg Chem 20:3705

    Article  Google Scholar 

  29. Doonan CJ, Slizys DA, Young CG (1999) J Am Chem Soc 121:6430

    Article  CAS  Google Scholar 

  30. Boyd IW, Spence JT (1982) Inorg Chem 21:1602

    Article  CAS  Google Scholar 

  31. Topich J, Lyon JT III (1984) Polyhedron 3:55

    Article  CAS  Google Scholar 

  32. Brown RE, Large RF (1971) In: Weissberger A, Rossiter B (eds) Electrochemical methods: physical methods in chemistry. Wiley-Interscience, New York, part IIA, chapter VI.

  33. Chaudhuri P, Hess M, Müller J, Hildenbrand K, Bill E, Weyhermüller T, Wieghardt K (1999) J Am Chem Soc 121:9599

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the Council of Scientific and Industrial Research (CSIR), New Delhi. Two of us (DM, and PBC) thank the CSIR for the award of research fellowships. RG also thanks DST, Government of India, for the award of a research grant (No. SR/FTP/CSA-01/2003).

Author information

Authors and Affiliations

  1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 700032, Kolkata, India

    Debdas Mandal, Rakesh Ganguly, Pabitra Baran Chatterjee & Muktimoy Chaudhury

  2. Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, 102-8554, Chiyoda-ku, Tokyo, Japan

    Akira Endo

  3. Department of Chemistry, University of Oregon, 97403, Eugene, OR, USA

    Timothy J. R. Weakley

Authors
  1. Debdas Mandal
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rakesh Ganguly
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pabitra Baran Chatterjee
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Akira Endo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Timothy J. R. Weakley
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Muktimoy Chaudhury
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Muktimoy Chaudhury.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mandal, D., Ganguly, R., Chatterjee, P.B. et al. cis-Dioxomolybdenum(VI) complexes of sterically encumbered phenol-based tetradentate N2O2 ligands: Structural, spectroscopic, and electrochemical studies. Struct Chem 18, 187–193 (2007). https://doi.org/10.1007/s11224-006-9078-1

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-006-9078-1

Keywords

Search

Navigation