Paul Chirik

Paul J. Chirik is an American chemist and currently the Edwards S. Sanford Professor of Chemistry at Princeton University.[1] He is the current Editor-in-Chief of Organometallics and an expert in sustainable chemistry and catalysis with Earth-abundant transition metals. [2][3]

Early life and career

Chirik was born in Philadelphia, Pennsylvania on June 13, 1973.[2] He graduated magna cum laude with a Bachelor's of Science in Chemistry in 1995 from Virginia Tech having conducted research with Joseph Merola.[4] He earned his Ph.D. with John Bercaw at Caltech studying the mechanism of metallocene-catalyzed olefin polymerization and hydrometallation chemistry in which he was recognized with the Hebert Newby McCoy Award.[5][6][7] After a brief postdoctoral appointment with Professor Christopher C. Cummins at the Massachusetts Institute of Technology[8] he joined the faculty at Cornell University in 2001 as an assistant professor.[2] In 2006, he was promoted to associate professor, and in 2009, he was named the Peter J. W. Debye Professor of Chemistry.[9]

In the course of his career, he has authored over 215 peer-reviewed, scientific publications,[3] and has been invited to give lectures and presentations in over 200 national and international seminars and conferences[9] including the 2012 Falling Walls Conference in Berlin, where he gave a talk entitled "Breaking the Wall of Sustainable Chemistry: How Modern Alchemy Can Lead to Inexpensive and Clean Technology".[10]

Research interests

Chirik has contributed to and popularized the field of catalysis with Earth-abundant Transition elements where iron and cobalt are used in place of precious metals such palladium, platinum and rhodium. Catalysts have been developed for applications in the pharmaceutical, flavor, fragrance, petrochemical, and fine chemical industries. One notable application is the preparation of commercial silicones with iron instead of platinum[11][12] in the hydrosilylation of alkenes.[11][13][14] Other notable applications have been in the areas of metal-ligand cooperativity, asymmetric hydrogenation,[12] hydrosilylation,[13] and hydroboration,[15] and cycloaddition[16][17] reactions.

Chirik has also developed Earth-abundant catalysts that operate in a more traditional sense, where the electron changes occur exclusively at the metal ("strong-field limit") with the judicious choice of the supporting ligand. This led to the development of catalysts for asymmetric hydrogenation,[18][19][20] hydrogen-isotope exchange,[21][22] C–H borylation[23] and cross coupling,[24] reactions that are of tremendous importance to the pharmaceutical industry.

Nitrogen functionalization and interconversion of ammonia with its elements

Chirik also has a research program in the interconversion of ammonia (NH3) with its constituent elements, N2 and H2. The forward reaction, where N2 is converted to ammonia and other value-added nitrogen-containing products is driven by the high carbon footprint associated with industrial ammonia synthesis by the Haber-Bosch process, whereas the reverse reaction, where ammonia is converted back into its elements, N2 and H2, is driven by the goal of developing carbon-neutral fuels.[25]

Using early transition metals with organic ligands to form a rationally designed coordination environment, Chirik has developed new routes to convert molecular nitrogen into value-added nitrogen-containing products.[26][27][28][29][30]

By utilizing proton-coupled electron transfer (PCET), Chirik has been able to cleave ammonia to form H2 using the concept of "coordination-induced weakening".[31][32][33]

Awards
  • Gabor Samorjai Award for Creative Research in Catalysis (2021)
  • Linus Pauling Medal (2020)
  • Eni Enviromental Solutions Prize (2019)
  • ICI Lectureship, University of Calgary (2018)
  • ACS Catalysis Lectureship for Advancement of Catalysis Science (2017)
  • Winner, Presidential Green Chemistry Challenge Award (2016)
  • Closs Lecturer, University of Chicago (2014)
  • Dalton Lecturer, University of California, Berkeley (2011)
  • Winner, Blavatnik Award for Young Scientists, NYAS (2009)
  • Arthur C. Cope Scholar Award, American Chemical Society (2009)
  • Bessel Fellow of the Alexander von Humboldt Foundation (2008)
  • Camille Dreyfus-Teacher Scholar (2006)
  • David and Lucile Packard Fellow in Science and Engineering (2004)
  • NSF CAREER Award (2003)
  • Herbert Newby McCoy Award for Outstanding Dissertation, Caltech (2000)

References
  1. "Paul Chirik | Princeton University Department of Chemistry". chemistry.princeton.edu.
  2. https://ecommons.cornell.edu/bitstream/1813/3196/1/CCB_074.pdf
  3. "The Chirik Group".
  4. "Group Alumni | Merola Group | Virginia Tech". www.merola.chem.vt.edu.
  5. "Former Bercaw Group Members". chemistry.caltech.edu.
  7. Chirik, Paul James (February 3, 2000). "Ancillary Ligand Effects on Fundamental Transformations in Metallocene Catalyzed Olefin Polymerization". California Institute of Technology – via Google Books.
  8. "Members | The Cummins Group". ccclab.mit.edu.
  10. Foundation, Falling Walls. "Paul Chirik | Falling Walls". falling-walls.com.
  11. Bart, Suzanne C.; Lobkovsky, Emil; Chirik, Paul J. (October 1, 2004). "Preparation and Molecular and Electronic Structures of Iron(0) Dinitrogen and Silane Complexes and Their Application to Catalytic Hydrogenation and Hydrosilation". Journal of the American Chemical Society. 126 (42): 13794–13807. doi:10.1021/ja046753t. PMID 15493939.
  12. Monfette, Sebastien; Turner, Zoë R.; Semproni, Scott P.; Chirik, Paul J. (March 14, 2012). "Enantiopure C1-Symmetric Bis(imino)pyridine Cobalt Complexes for Asymmetric Alkene Hydrogenation". Journal of the American Chemical Society. 134 (10): 4561–4564. doi:10.1021/ja300503k. PMID 22390262.
  13. Chirik, Paul J.; Delis, Johannes G. P.; Lewis, Kenrick M.; Nye, Susan A.; Weller, Keith J.; Atienza, Crisita Carmen Hojilla; Tondreau, Aaron M. (February 3, 2012). "Iron Catalysts for Selective Anti-Markovnikov Alkene Hydrosilylation Using Tertiary Silanes". Science. 335 (6068): 567–570. Bibcode:2012Sci...335..567T. doi:10.1126/science.1214451. PMID 22301315. S2CID 27639869.
  14. Rosner, Hillary (October 15, 2012). "Modern-Day Alchemy Has Iron Working Like Platinum" – via NYTimes.com.
  15. Obligacion, Jennifer V.; Chirik, Paul J. (December 26, 2013). "Bis(imino)pyridine Cobalt-Catalyzed Alkene Isomerization–Hydroboration: A Strategy for Remote Hydrofunctionalization with Terminal Selectivity". Journal of the American Chemical Society. 135 (51): 19107–19110. doi:10.1021/ja4108148. PMID 24328236.
  16. Russell, Sarah K.; Lobkovsky, Emil; Chirik, Paul J. (June 15, 2011). "Iron-Catalyzed Intermolecular [2π + 2π] Cycloaddition". Journal of the American Chemical Society. 133 (23): 8858–8861. doi:10.1021/ja202992p. PMID 21598972.
  17. Chirik, Paul J.; Tondreau, Aaron M.; Schmidt, Valerie A.; Hoyt, Jordan M. (August 28, 2015). "Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes". Science. 349 (6251): 960–963. Bibcode:2015Sci...349..960H. doi:10.1126/science.aac7440. PMID 26315433. S2CID 206640239.
  18. Chirik, Paul J.; Tudge, Matthew T.; Krska, Shane W.; Hoyt, Jordan M.; Shevlin, Michael; Friedfeld, Max R. (November 29, 2013). "Cobalt Precursors for High-Throughput Discovery of Base Metal Asymmetric Alkene Hydrogenation Catalysts". Science. 342 (6162): 1076–1080. Bibcode:2013Sci...342.1076F. doi:10.1126/science.1243550. PMID 24288328. S2CID 13735246.
  19. Borman, Stu. "Catalysts That Are Less Precious | December 16, 2013 Issue - Vol. 91 Issue 50 | Chemical & Engineering News". cen.acs.org.
  20. Chirik, Paul J.; Shevlin, Michael; Ruck, Rebecca T.; Zhong, Hongyu; Friedfeld, Max R. (May 25, 2018). "Cobalt-catalyzed asymmetric hydrogenation of enamides enabled by single-electron reduction". Science. 360 (6391): 888–893. Bibcode:2018Sci...360..888F. doi:10.1126/science.aar6117. PMID 29798879.
  21. Chirik, Paul J.; Pelczer, István; Rivera, Nelo; Hesk, David; Yu, Renyuan Pony (January 3, 2016). "Iron-catalysed tritiation of pharmaceuticals". Nature. 529 (7585): 195–199. Bibcode:2016Natur.529..195P. doi:10.1038/nature16464. PMID 26762456. S2CID 4382943.
  22. "'Radiolabeling' lets scientists track the breakdown of drugs | Princeton University Department of Chemistry". chemistry.princeton.edu.
  23. Obligacion, Jennifer V.; Semproni, Scott P.; Chirik, Paul J. (March 19, 2014). "Cobalt-Catalyzed C–H Borylation". Journal of the American Chemical Society. 136 (11): 4133–4136. doi:10.1021/ja500712z. PMID 24588541.
  24. Neely, Jamie M.; Bezdek, Máté J.; Chirik, Paul J. (December 28, 2016). "Insight into Transmetalation Enables Cobalt-Catalyzed Suzuki–Miyaura Cross Coupling". ACS Central Science. 2 (12): 935–942. doi:10.1021/acscentsci.6b00283. PMC 5200927. PMID 28058283.
  25. Vegge, Tejs; Nørskov, Jens K.; Christensen, Claus Hviid; Klerke, Asbjørn (May 7, 2008). "Ammonia for hydrogen storage: challenges and opportunities". Journal of Materials Chemistry. 18 (20): 2304–2310. doi:10.1039/B720020J.
  26. "CU researchers find long-sought method for fixing nitrogen". Cornell Chronicle.
  27. "'Remarkable chemical transformation,' new method for converting nitrogen to ammonia, is discovered by Cornell researchers". Cornell Chronicle.
  28. "Chemists make nitrogen-carbon bonds but skip the ammonia". Cornell Chronicle.
  29. Chirik, Paul J.; Lobkovsky, Emil; Knobloch, Donald J. (January 3, 2010). "Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex". Nature Chemistry. 2 (1): 30–35. Bibcode:2010NatCh...2...30K. doi:10.1038/nchem.477. PMID 21124377.
  30. Semproni, Scott P.; Chirik, Paul J. (July 31, 2013). "Synthesis of a Base-Free Hafnium Nitride from N2 Cleavage: A Versatile Platform for Dinitrogen Functionalization". Journal of the American Chemical Society. 135 (30): 11373–11383. doi:10.1021/ja405477m. PMID 23829435.
  31. Pappas, Iraklis; Chirik, Paul J. (March 18, 2015). "Ammonia Synthesis by Hydrogenolysis of Titanium–Nitrogen Bonds Using Proton Coupled Electron Transfer". Journal of the American Chemical Society. 137 (10): 3498–3501. doi:10.1021/jacs.5b01047. PMID 25719966.
  32. Chirik, Paul J.; Guo, Sheng; Bezdek, Máté J. (November 11, 2016). "Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex". Science. 354 (6313): 730–733. Bibcode:2016Sci...354..730B. doi:10.1126/science.aag0246. PMID 27846601.
  33. Margulieux, Grant W.; Bezdek, Máté J.; Turner, Zoë R.; Chirik, Paul J. (May 3, 2017). "Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand". Journal of the American Chemical Society. 139 (17): 6110–6113. doi:10.1021/jacs.7b03070. PMID 28414434.
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