Award Abstract # 2102192
CAS: Taming the Reactivity of Base Metal Hydrides Through Bifunctional Ligands

NSF Org: CHE
Division Of Chemistry
Recipient: CINCINNATI UNIV OF
Initial Amendment Date: July 21, 2021
Latest Amendment Date: July 19, 2022
Award Number: 2102192
Award Instrument: Continuing Grant
Program Manager: Geroge Richter-Addo
CHE
 Division Of Chemistry
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: September 1, 2021
End Date: August 31, 2024 (Estimated)
Total Intended Award Amount: $500,000.00
Total Awarded Amount to Date: $500,000.00
Funds Obligated to Date: FY 2021 = $160,540.00
FY 2022 = $339,460.00
History of Investigator:
  • Hairong Guan (Principal Investigator)
    hairong.guan@uc.edu
Recipient Sponsored Research Office: University of Cincinnati Main Campus
2600 CLIFTON AVE
CINCINNATI
OH  US  45220-2872
(513)556-4358
Sponsor Congressional District: 01
Primary Place of Performance: University of Cincinnati Main Campus
301 Clifton Court
Cincinnati
OH  US  45221-0172
Primary Place of Performance
Congressional District:
01
Unique Entity Identifier (UEI): DZ4YCZ3QSPR5
Parent UEI: DZ4YCZ3QSPR5
NSF Program(s): Chemical Catalysis
Primary Program Source: 01002122DB NSF RESEARCH & RELATED ACTIVIT
01002223DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 090Z, 8037, 8396, 8398
Program Element Code(s): 688400
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Hairong Guan of the University of Cincinnati will study molecules with metal-hydrogen bonds (i.e., metal hydrides) as catalysts for the hydrogenation or reduction of fatty acid methyl esters, carbon dioxide, and sugar-derived polyols. These catalytic processes are highly desirable to the chemical industry that manufactures surfactants used in many consumer products, and converts renewable materials to fuels and value-added chemicals. This project will focus on the use of earth-abundant, inexpensive metals such as manganese, iron, cobalt, nickel, and copper to design such catalysts. To enhance the reactivity of the metal hydrides and to minimize degradation of the catalysts, ligands that not only participate in hydrogen transfer but also bind tightly to the metals will be employed. The project will contribute to the rigorous training of a diverse group of high school, undergraduate, and graduate students via a number of programs including the American Chemical Society Project SEED Program, the NSF Research Experience for Undergraduates program, and the University of Cincinnati?s Women in Science and Engineering (WISE) Program. Through this project, Professor Guan will also develop research-based materials for a laboratory course that can be used by community colleges or institutions with limited resources, provide research opportunities to underrepresented minority students, and enhance student professional development through collaborations with local chemical companies.

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Hairong Guan of the University of Cincinnati will study the strategies of improving the reactivity of base metal hydrides, which are key intermediates in many hydrogenation or reduction processes. Bifunctional and strongly chelating ligands will be designed under the hypothesis that they can deemphasize the roles played by the metals, participate in two-electron transfer, or suppress cluster formation. The specific research objectives include the development of more robust and active hydrogenation catalysts based on iron and nickel, the design of hydroxycyclopentadienyl complexes of manganese and cobalt as masked metal hydrides, and the pursuit of phosphine-ligated mononuclear copper hydrides. In support of the broader impacts of the project, Professor Guan will actively engage in programs focusing on providing research opportunities to underrepresented minority students including those from collaborating primarily undergraduate institutions. Research-based teaching materials will be disseminated more broadly in the chemical education literature and to other institutions. Active collaborations with local companies will be geared toward enhancing student problem-solving skills in an industrial setting.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 11)
Adhikary, Anubendu and Saha, Sayantani and Kumar, N. Sai and Oliver, Allen G. and Krause, Jeanette A. and Guan, Hairong "Pitfalls for POCOP-Type Palladium Pincer Complexes in Catalytic Reduction of CO 2 with Catecholborane" Organometallics , v.42 , 2023 https://doi.org/10.1021/acs.organomet.3c00126 Citation Details
Ahmadianpoor, Mahmood and Pridemore, Patrick D and Krause, Jeanette A and Guan, Hairong "Effect of backbone linker (O vs NH) on the ability of pincer-supported nickel hydrides to reduce CO2" Journal of Organometallic Chemistry , v.1022 , 2024 https://doi.org/10.1016/j.jorganchem.2024.123399 Citation Details
Collett, Joel D. and Krause, Jeanette A. and Guan, Hairong "Nickel Hydride Complexes Supported by a Pyrrole-Derived Phosphine Ligand" Organometallics , v.41 , 2022 https://doi.org/10.1021/acs.organomet.1c00694 Citation Details
Le, Nghia and Chuang, Natalie L. and Oliver, Clay M. and Samoshin, Andrey V. and Hemphill, Jack T. and Morris, Kelsey C. and Hyland, Stephen N. and Guan, Hairong and Webster, Charles Edwin and Clark, Timothy B. "Hidden Role of Borane in Directed CH Borylation: Rate Enhancement through Autocatalysis" ACS Catalysis , 2023 https://doi.org/10.1021/acscatal.3c03316 Citation Details
Mokhtar, Mennatullah M. and Andersen, Joel M. and Kister, Ethan A. and Hopkins, Jordan X. and Estier, Tom and Hamilton, Fiona and Guan, Hairong and Mack, James and Haley, Rebecca A. "A Mechanistic Perspective on the Mechanochemical Method To Reduce Carbonyl Groups with Stainless Steel and Water" European Journal of Organic Chemistry , v.26 , 2023 https://doi.org/10.1002/ejoc.202300149 Citation Details
Pandey, Bedraj and Krause, Jeanette A and Guan, Hairong "Cobalt-Catalyzed Additive-Free Dehydrogenation of Neat Formic Acid" ACS Catalysis , v.14 , 2024 https://doi.org/10.1021/acscatal.4c04109 Citation Details
Pandey, Bedraj and Krause, Jeanette A. and Guan, Hairong "Iron Dihydride Complex Stabilized by an All-Phosphorus-Based Pincer Ligand and Carbon Monoxide" Inorganic Chemistry , 2022 https://doi.org/10.1021/acs.inorgchem.2c01027 Citation Details
Pandey, Bedraj and Krause, Jeanette A. and Guan, Hairong "Methyl Effects on the Stereochemistry and Reactivity of PPP-Ligated Iron Hydride Complexes" Inorganic Chemistry , v.62 , 2023 https://doi.org/10.1021/acs.inorgchem.2c03803 Citation Details
Pandey, Bedraj and Krause, Jeanette A. and Guan, Hairong "On the Demise of PPP-Ligated Iron Catalysts in the Formic Acid Dehydrogenation Reaction" Inorganic Chemistry , v.62 , 2023 https://doi.org/10.1021/acs.inorgchem.3c03125 Citation Details
Saha, Sayantani and Krause, Jeanette A and Guan, Hairong "C(sp)H, SH, and SnH Bond Activation with a Cobalt(I) Pincer Complex" Inorganic Chemistry , v.63 , 2024 https://doi.org/10.1021/acs.inorgchem.4c01993 Citation Details
Xu, Vivian and Pandey, Bedraj and Jayawardhena, J. P. and Krause, Jeanette A. and Guan, Hairong "The curious cases of tetrahydrosalen-type ligands interacting with Ni( ii ): structures and ligand-based oxidation reactions" Dalton Transactions , v.52 , 2023 https://doi.org/10.1039/d3dt02023a Citation Details
(Showing: 1 - 10 of 11)

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Metal-based catalysts play indispensable roles in chemical synthesis for pharmaceutical, energy, and materials applications. The objective of this research project was to develop effective strategies to modulate the reactivity of molecules bearing an earth-abundant metal bound to hydrogen atom (also known as base metal hydrides), which are key intermediates in many catalytic processes such as hydrogenation and dehydrogenation reactions.  Research efforts funded by this NSF award has deepened the understanding of how spatial arrangement, donor properties, and linkage atoms of the supporting ligands affect the ability of base metal hydrides to transfer the hydride to substrates, and ultimately their catalytic performance.  Catalytic reactions that have been studied extensively in this project include reduction of carbon dioxide, a greenhouse gas, and dehydrogenation of formic acid, a hydrogen-storage material.  Research supported by this NSF award has also uncovered unique copper hydride clusters that can help understand how atomically precise nanoclusters grow and decay in solution.           

The research activities have proven an effective training and outreach tool by involving five undergraduate students including one NSF-REU student and one visiting student, one high school student, and eight graduate students.  To further integrate research into undergraduate training, an open-ended research project format has been further developed at the University of Cincinnati and adopted by instructors at several primarily undergraduate institutions (PUIs).  The research project also involves collaborations with PUIs that have led to two joint publications.  

 


Last Modified: 12/11/2024
Modified by: Hairong Guan

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