The drover group
WESTERN UNIVERSITY, LONDON, ON
Research Program:
NEW TECHNOLOGY FOR SUSTAINABLE ENERGY
Research in my group bridges the traditional limits of synthetic inorganic and organic chemistry, with an overarching goal to develop new functional molecules: ligands, transition metal, and main group compounds that promote the equitable use of resources, specifically with regard to global hydrogen, carbon, nitrogen, and oxygen cycles. This research program tackles grand challenges in small-molecule activation with interests in chemical synthesis and materials science.
current directions
|
i. Fuels From Waste: Achieving Selectivity in CO₂ Reduction: Despite the abundance of CO₂ in Earth’s atmosphere, catalytic transformations of this molecule currently focus on reduction to formate (HCO₂⁻) or carbon monoxide (CO) - representing a bottleneck for accessing reduced C₁-equivalents such as methanol (CH₃OH) directly. We aim to identify new iron catalysts for the selective reduction of CO₂, a waste/greenhouse gas, to CH₃OH. |
|
|
ii. New Avenues in Dihydrogen Chemistry: Oxidation, Activation, and Storage: Given increased global demand on energy, finding an alternative to fossil fuel combustion is requisite. The management of electron equivalents between H₂ and H⁺ via oxidation has been considered a modern solution to this problem, delivering clean energy in the form of H₂ fuel cells. To date, the golden standard for H₂ oxidation (HOR) is Pt-metal – a high cost material that is also employed by the automotive industry. We seek to find a cheap base metal alternative. |
|
SUMMARY OF RECENT RESEARCH PROGRESS
Updated February 2, 2022
Designing Ligands with Lewis Acidic Secondary Coordination Spheres:
Diphosphine ligands have found great applicability in the realm of synthetic chemistry, with modifications to backbone length and R substituent leading to dramatic improvements in performance, selectivity, and net reactivity. Recently, our group at UWindsor disclosed the preparation and synthesis of a new ambiphilic diphosphine ligand, 1,2-bis(di(3-dicyclohexylpropylboranyl)phosphino)ethane a boron-rich scaffold that boasts tetraboranyl functionality.
References:
• Chem. -Eur. J. 2020, 26, 11180-11186. DOI: 10.1002/chem.202001218
• Dalton Trans. 2020, 49, 16312-16318. DOI: 10.1039/D0DT00963F
• Inorg. Chem. 2021, 60, 37-41. DOI: 10.1021/acs.inorgchem.0c03409
• Organometallics 2021, 40, 2450-2457. DOI: 10.1021/acs.organomet.1c00194
• Dalton Trans. 2021, 50, 12440-12447. DOI: 10.1039/D1DT02331D
• Chem. -Eur. J. 2021, 27, 16021-16027. DOI. 10.1002/chem.202103121
• Chem. Commun. 2022, 58, 68-71. DOI: 10.1039/D1CC06064C
• Chem. Commun. 2022, 58, 2500-2503. DOI: 10.1039/D1CC07060F
• J. Coord. Chem. 2022, ASAP. DOI: 10.1080/00958972.2022.2067989
• Trends Chem. 2022, 4, 331-346. DOI: 10.1016/j.trechm.2022.01.007
• Chem. Soc. Rev. 2022, 51, 1861-1880. DOI: 10.1039/D2CS00022A
Diphosphine ligands have found great applicability in the realm of synthetic chemistry, with modifications to backbone length and R substituent leading to dramatic improvements in performance, selectivity, and net reactivity. Recently, our group at UWindsor disclosed the preparation and synthesis of a new ambiphilic diphosphine ligand, 1,2-bis(di(3-dicyclohexylpropylboranyl)phosphino)ethane a boron-rich scaffold that boasts tetraboranyl functionality.
References:
• Chem. -Eur. J. 2020, 26, 11180-11186. DOI: 10.1002/chem.202001218
• Dalton Trans. 2020, 49, 16312-16318. DOI: 10.1039/D0DT00963F
• Inorg. Chem. 2021, 60, 37-41. DOI: 10.1021/acs.inorgchem.0c03409
• Organometallics 2021, 40, 2450-2457. DOI: 10.1021/acs.organomet.1c00194
• Dalton Trans. 2021, 50, 12440-12447. DOI: 10.1039/D1DT02331D
• Chem. -Eur. J. 2021, 27, 16021-16027. DOI. 10.1002/chem.202103121
• Chem. Commun. 2022, 58, 68-71. DOI: 10.1039/D1CC06064C
• Chem. Commun. 2022, 58, 2500-2503. DOI: 10.1039/D1CC07060F
• J. Coord. Chem. 2022, ASAP. DOI: 10.1080/00958972.2022.2067989
• Trends Chem. 2022, 4, 331-346. DOI: 10.1016/j.trechm.2022.01.007
• Chem. Soc. Rev. 2022, 51, 1861-1880. DOI: 10.1039/D2CS00022A
Expanding the Hydride Donor Toolbox:
Hydride transfer reactions are ubiquitous in chemistry, mediating challenging reductions of a range of organic and inorganic substrates. As a result, steady advances have been made not only in substrate scope, but also in regards to reagent design/methodology, whereby reactive fragments with low hydricity values continue to be targeted to encourage delivery, in some instances, cooperatively with a bound ligand. Detailed characterization of these reagents continues to be an important challenge of broad interest.
References:
• Inorg. Chem. 2021, 60, 37-41. DOI: 10.1021/acs.inorgchem.0c03409
• Organometallics 2021, 40, 2450-2457. DOI: 10.1021/acs.organomet.1c00194
• Dalton Trans. 2021, 50, 12440-12447. DOI: 10.1039/D1DT02331D
Hydride transfer reactions are ubiquitous in chemistry, mediating challenging reductions of a range of organic and inorganic substrates. As a result, steady advances have been made not only in substrate scope, but also in regards to reagent design/methodology, whereby reactive fragments with low hydricity values continue to be targeted to encourage delivery, in some instances, cooperatively with a bound ligand. Detailed characterization of these reagents continues to be an important challenge of broad interest.
References:
• Inorg. Chem. 2021, 60, 37-41. DOI: 10.1021/acs.inorgchem.0c03409
• Organometallics 2021, 40, 2450-2457. DOI: 10.1021/acs.organomet.1c00194
• Dalton Trans. 2021, 50, 12440-12447. DOI: 10.1039/D1DT02331D
Nickel-mediated Cross-Coupling:
The elementary steps of metal-mediated catalysis e.g., oxidative addition, transmetalation, and reductive elimination continue to interest a broad audience due to importance in designing superior routes into specialty chemicals, pharmaceuticals, and agrochemicals. From such fundamental studies, steady advances have been made in tailoring ligand design with an eye toward developing reactive systems for both bond cleavage and formation reactions. In this aspect of our program, we advance understanding of oxidative addition at coordinatively saturated organometallic complexes and provide new opportunities for bond activation. These contributions concern the Lewis acid-promoted oxidative addition of iodoarenes using a coordinatively saturated Ni(0) complex bearing a diphosphine ligand, recently reported by our group - P2BCy4 = 1,2-bis(di(3-dicyclohexylboranyl)propylphosphino)ethane. Later, we expanded upon this study through an in-depth investigation using gold transmetalation reagents.
References:
• Chem. -Eur. J. 2021, 27, 16021-16027. DOI. 10.1002/chem.202103121
• Chem. Commun. 2022, 58, 68-71. DOI: 10.1039/D1CC06064C
The elementary steps of metal-mediated catalysis e.g., oxidative addition, transmetalation, and reductive elimination continue to interest a broad audience due to importance in designing superior routes into specialty chemicals, pharmaceuticals, and agrochemicals. From such fundamental studies, steady advances have been made in tailoring ligand design with an eye toward developing reactive systems for both bond cleavage and formation reactions. In this aspect of our program, we advance understanding of oxidative addition at coordinatively saturated organometallic complexes and provide new opportunities for bond activation. These contributions concern the Lewis acid-promoted oxidative addition of iodoarenes using a coordinatively saturated Ni(0) complex bearing a diphosphine ligand, recently reported by our group - P2BCy4 = 1,2-bis(di(3-dicyclohexylboranyl)propylphosphino)ethane. Later, we expanded upon this study through an in-depth investigation using gold transmetalation reagents.
References:
• Chem. -Eur. J. 2021, 27, 16021-16027. DOI. 10.1002/chem.202103121
• Chem. Commun. 2022, 58, 68-71. DOI: 10.1039/D1CC06064C
Ambiphilic Ligand Design:
Owing to applicability in materials sciences, catalysis, frustrated Lewis-pair (FLP) chemistry, and as
building blocks in molecular and supramolecular synthetic chemistry, main group heterocycles have evolved
as targets of intrigue. This component of our work seeks to prepare unusual ring systems with donor and acceptor functionality in the same contiguous ring system - a sought-after structural type that has previously found application in frustrated Lewis pair systems (G. Erker 2019, 2020). Notwithstanding, the construction of such ring systems is challenging and is often accompanied by the formation of unproductive Lewis acid/base adducts, which thwart ring closure.
References:
• Chem. Commun. 2022, ASAP. DOI: 10.1039/D1CC07060F
Owing to applicability in materials sciences, catalysis, frustrated Lewis-pair (FLP) chemistry, and as
building blocks in molecular and supramolecular synthetic chemistry, main group heterocycles have evolved
as targets of intrigue. This component of our work seeks to prepare unusual ring systems with donor and acceptor functionality in the same contiguous ring system - a sought-after structural type that has previously found application in frustrated Lewis pair systems (G. Erker 2019, 2020). Notwithstanding, the construction of such ring systems is challenging and is often accompanied by the formation of unproductive Lewis acid/base adducts, which thwart ring closure.
References:
• Chem. Commun. 2022, ASAP. DOI: 10.1039/D1CC07060F
methods
All synthesized complexes, transient intermediates, and molecules of interest will be characterized using a suite of physical inorganic spectroscopic methods including: nuclear magnetic resonance (NMR), electron-paramagnetic resonance (EPR), Mössbauer (for ⁵⁷Fe), mass spectrometry (MS), infrared/Raman, and UV-Visible spectroscopies. Single crystal X-ray diffraction (XRD) will be additionally employed to ascertain solid-state molecular geometry.
Training in the areas of synthetic inorganic chemistry including the use of anaerobic techniques (glovebox and Schlenk line manipulation) will be acquired. A high-vac line for the manipulation of gases (CO₂ and H₂), and a bulk cell for the electrochemical study of catalysts under variable temperature and pressure will also be employed.
Training in the areas of synthetic inorganic chemistry including the use of anaerobic techniques (glovebox and Schlenk line manipulation) will be acquired. A high-vac line for the manipulation of gases (CO₂ and H₂), and a bulk cell for the electrochemical study of catalysts under variable temperature and pressure will also be employed.
FUNDING
- The University of Windsor 2019 - 2023
- NSERC Discovery Grant (RGPIN-2020-04480) 2020-2025
- NSERC Discovery Launch Supplement (DGECR-2020-00183) 2020-2025
- Canadian Foundation for Innovation John Evans Leadership Find (CFI-JELF) (Project 41099) 2021
- The American Chemical Society Petroleum Research Fund (ACS-PRF) New Directions (PRF# 62284-ND3) 2021-2022
- WeSPARK Igniting Discovery Grant 2021
- eCampus Ontario Virtual Learning Strategy Grant (Humanizing Learning) 2021
- The University of Windsor Undergraduate Research Award (URE) 2021
- The University of Windsor IGNITE program 2019-Present
- The University of Windsor CRISP/Outstanding Scholars Program 2020-Present
- The University of Windsor Research Stimulus Fund 2021-Present
- Ontario Research Fund (ORF) - Research Infrastructure (Small Infrastructure) 2022
- Imperial Oil Research Award 2022-2025
- MITACS Globallink 2022 (x2)
- NSERC Alliance Missions 2022-2024
- NSERC Alliance International Catalyst 2022-2023
- NSERC Alliance with Imperial Oil Ltd. 2022-2025
- UW Faculty of Engineering Innovating Sustainability Grant (w/ Prof. Ofelia Jianu) 2022-2024
- Student Prizes: NSERC USRA/CGS-M/CGS-D/Vanier, Ontario Graduate Scholarship, CIC AURIC award. 2019-
- Western University, 2023 - Present
- Ontario Early Researcher Award (ERA-R19), 2024-Present
- Western Interdisciplinary Development Initiative, 2024-2025
|
|
|
|
|
|