Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.


Bifunctional beginnings

In the early 1980s, Shvo and co-workers reported a molecular ruthenium complex that was active in the catalytic dehydrogenation of alcohols and the hydrogenation of carbonyl compounds. Although the reactions themselves were already known, the ligand represented a new paradigm in bond formation/breaking processes that influences homogeneous catalysis to this day.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it


Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Cooperativity in complexes of bifunctional cyclopentadienone/hydroxycyclopentadienyl ligands was discovered by Shvo and co-workers and has been harnessed in diverse transformations.


  1. Khusnutdinova, J. R. & Milstein, D. Metal–ligand cooperation. Angew. Chem. Int. Ed. 54, 12236–12273 (2015).

    Article  CAS  Google Scholar 

  2. Blum, Y. & Shvo, Y. Catalytically reactive ruthenium intermediates in the homogeneous oxidation of alcohols to esters. Isr. J. Chem. 24, 144–148 (1984).

    Article  CAS  Google Scholar 

  3. Shvo, Y., Czarkie, D., Rahamim, Y. & Chodosh, D. F. A new group of ruthenium complexes: structure and catalysis. J. Am. Chem. Soc. 108, 7400–7402 (1986).

    Article  CAS  Google Scholar 

  4. Blum, Y., Czarkie, D., Rahamim, Y. & Shvo, Y. (Cyclopentadienone)ruthenium carbonyl complexes — a new class of homogeneous hydrogenation catalysts. Organometallics 4, 1459–1461 (1985).

    Article  CAS  Google Scholar 

  5. Conley, B. L., Pennington-Boggio, M. K., Boz, E. & Williams, T. J. Discovery, applications, and catalytic mechanisms of Shvo’s catalyst. Chem. Rev. 110, 2294–2312 (2010).

    Article  CAS  Google Scholar 

  6. Gusev, D. G. & Spasyuk, D. M. Revised mechanisms for aldehyde disproportionation and the related reactions of the Shvo catalyst. ACS Catal. 8, 6851–6861 (2018).

    Article  CAS  Google Scholar 

  7. Dub, P. A. & Gordon, J. C. Metal–ligand bifunctional catalysis: the “accepted” mechanism, the issue of concertedness, and the function of the ligand in catalytic cycles involving hydrogen atoms. ACS Catal. 7, 6635–6655 (2017).

    Article  CAS  Google Scholar 

  8. Dong, G., Teo, P., Wickens, Z. K. & Grubbs, R. H. Primary alcohols from terminal olefins: formal anti-Markovnikov hydration via triple relay catalysis. Science 333, 1609–1612 (2011).

    Article  CAS  Google Scholar 

  9. Casey, C. P. & Guan, H. An efficient and chemoselective iron catalyst for the hydrogenation of ketones. J. Am. Chem. Soc. 129, 5816–5817 (2007).

    Article  CAS  Google Scholar 

  10. Higashi, T., Ando, H., Kusumoto, S. & Nozaki, K. Metal-ligand cooperative C–H bond formation by cyclopentadienone platinum complexes. J. Am. Chem. Soc. 141, 2247–2250 (2019).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations


Corresponding author

Correspondence to Rosie J. Somerville.

Ethics declarations

Competing interests

The author declares no competing interests.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Somerville, R.J. Bifunctional beginnings. Nat Rev Chem 5, 518–519 (2021).

Download citation

  • Published:

  • Issue Date:

  • DOI:


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing