Paul Chirik

Paul J. Chirik is an American chemist and currently holds the position of Edwards S. Sanford Professor of Chemistry at Princeton University.[1] His expertise is in the field of Organometallic chemistry, particularly in sustainable and environmentally-friendly catalysis with earth abundant elements.[2][3] In 2015, he was appointed Editor-in-Chief of Organometallics, a peer-reviewed journal published by the American Chemical Society.[4][5][6][7] He has mentored over 30 PhD students and 20 postdoctoral associates.[1] He has won several awards, including the Arthur C. Cope Scholar Award,[8] the Blavatnik Award for Young Scientists,[9] a Packard Fellowship in science and engineering,[10] a Camille Dreyfus Teacher Scholar Award,[11] an NSF Career Award,[12] and a Presidential Green Chemistry Challenge Award.[13]

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.[14] 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.[15][16][17] After a brief postdoctoral appointment with Professor Christopher C. Cummins at the Massachusetts Institute of Technology[18] 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.[19]

In the course of his career, he has authored over 180 peer-reviewed, scientific publications,[3] is inventor on over 15 patents and has been invited to give lectures and presentations in over 200 national and international seminars and conferences[19] 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".[20]

Research interests

Chirik has contributed to the field of catalysis with earth abundant Transition elements such as iron and cobalt, with the ultimate goal to free the pharmaceutical and other industries from overdependence on the scarce and expensive rare earth catalysts that are presently and commonly used. His group has utilized redox-active ligands[21] to control electron flow with first row transition metals to enable multielectron chemistry. Chirik's catalysts are of interest for asymmetric hydrogenation[22][23] and hydrosilylation of alkenes.[22][24][25]

Chirik's research lies at the intersection of Organic and Inorganic chemistry and involves the development of sustainable methods in chemical synthesis. His research group explores the concept of "modern alchemy", whereby ligand design is used to transmute the reactivity of earth-abundant metals to mimic, or ideally surpass, the performance of precious metals. His group tackles pharmaceutically- and industrially-relevant problems using a combination of synthetic, spectroscopic, physical characterization and computational methods. The major research areas in his laboratory are catalysis with Earth-abundant metals, dinitrogen functionalization, and the interconversion of ammonia with its elements.[1][3]

Catalysis with Earth-abundant metals

The core of Chirik's Earth-abundant metal catalysis program is the understanding and manipulation of electron flow, and its application to solving modern problems. Development efforts are specifically geared towards problems in the pharmaceutical, flavor, fragrance, petrochemical, and silicones industries. The broad catalysis concept of "metal-ligand cooperativity" popularized by Chirik, where electron changes occur concomitantly between the metal and the supporting ligand ("redox-active limit"), led to the development of Earth-abundant catalysts based on iron and cobalt for asymmetric hydrogenation,[23] hydrosilylation,[24] and hydroboration[26] of olefins with superior activities and selectivities to their precious metal counterparts as well as catalysts for unprecedented cycloaddition[27][28] 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,[29][30][31] hydrogen-isotope exchange,[32][33] C–H borylation[34] and cross coupling,[35] 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.[36]

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.[37][38][39][40][41]

By utilizing proton-coupled electron transfer (PCET), Chirik has been able to cleave ammonia to form H2 using the concept of "coordination-induced weakening".[42][43][44]

Awards

  • ICI Lectureship, University of Calgary (2018)
  • ACS Catalysis Lectureship for Advancement of Catalysis Science (2017)
  • Winner, Presidential Green Chemistry Challenge Award (2016)
  • First JSCC International Award for Creative Work (2015)
  • 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)
  • Stephen and Margery Russell Distinguished Teaching Award (2005)
  • 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. "Organometallics welcomes new editor-in-chief: Paul Chirik, Ph.D." American Chemical Society.
  5. "Paul Chirik To Lead Organometallics | Chemical & Engineering News". cen.acs.org.
  6. "Paul Chirik (PhD '00) Named Editor of Organometallics". Caltech Alumni Association.
  7. "Chirik named new editor-in-chief of Organometallics | Princeton University Department of Chemistry". chemistry.princeton.edu.
  8. "Paul Chirik: Arthur C. Cope Scholar Awardee | March 9, 2009 Issue - Vol. 87 Issue 10 | Chemical & Engineering News". cen.acs.org.
  9. "Paul Chirik | Blavatnik Awards for Young Scientists". blavatnikawards.org.
  10. "Chirik, Paul J."
  11. "Dreyfus Foundation | Dedicated to the advancement of the chemical sciences".
  12. "Cornell's Paul Chirik wins national research award". Cornell Chronicle.
  13. US EPA, OCSPP (June 7, 2016). "Presidential Green Chemistry Challenge: 2016 Academic Award". US EPA.
  14. "Group Alumni | Merola Group | Virginia Tech". www.merola.chem.vt.edu.
  15. "Former Bercaw Group Members". chemistry.caltech.edu.
  16. Chirik, Paul James (February 3, 2000). "Ancillary Ligand Effects on Fundamental Transformations in Metallocene Catalyzed Olefin Polymerization". California Institute of Technology via Google Books.
  17. "Members | The Cummins Group". ccclab.mit.edu.
  18. Foundation, Falling Walls. "Paul Chirik | Falling Walls". falling-walls.com.
  19. "Non-innocent ligand". December 11, 2018 via Wikipedia.
  20. 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.
  21. 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.
  22. 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.
  23. Rosner, Hillary (October 15, 2012). "Modern-Day Alchemy Has Iron Working Like Platinum" via NYTimes.com.
  24. 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.
  25. 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.
  26. 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.
  27. 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.
  28. Borman, Stu. "Catalysts That Are Less Precious | December 16, 2013 Issue - Vol. 91 Issue 50 | Chemical & Engineering News". cen.acs.org.
  29. 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.
  30. 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.
  31. "'Radiolabeling' lets scientists track the breakdown of drugs | Princeton University Department of Chemistry". chemistry.princeton.edu.
  32. 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.
  33. 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.
  34. 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.
  35. "CU researchers find long-sought method for fixing nitrogen". Cornell Chronicle.
  36. "'Remarkable chemical transformation,' new method for converting nitrogen to ammonia, is discovered by Cornell researchers". Cornell Chronicle.
  37. "Chemists make nitrogen-carbon bonds but skip the ammonia". Cornell Chronicle.
  38. 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.
  39. 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.
  40. 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.
  41. 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.
  42. 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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