Affordable and Clean Energy (SDG 7), Responsible Consumption and Production (SDG 12) Green Chemistry Approaches to Base Metal Catalyst Design: Leveraging a Lewis Acidic Secondary Coordination Sphere for Small Molecule Activation Marissa L. Clapson Department of Chemistry, University of Prince Edward Island 550 University Avenue, Charlottetown, Prince Edward Island, C1A 4P3. *mlclapson@upei.ca Chemistry is experiencing a call to action concerning the development and implementation of sustainable chemical processes and transformations. 1 The development of base metal catalysts, in place of their precious metal counterparts, is one method to reduce both cost and toxicity while opening avenues for novel reactivity. 2 In recent years, pincer complexes have shown remarkable catalytic activity. 3 Iron, cobalt, and nickel hydride species featuring strongly trans -influencing, anionic central donor atoms (PCP, POCOP, PSiP, PBP) have been shown to rapidly insert CO 2 into the metal-hydride (M-H) bond later resulting in the formation of formate. 4 However, CO 2 Green chemistry approaches to base metal catalyst design: leveraging a lewis acidic secondary coordination sphere for small molecule activation Marissa L. Clapson Department of Chemistry, University of Prince Edward Island 550 University Avenue, Charlottetown, Prince Edward Island, C1A 4P3. * mlclapson@upei.ca Chemistry is experiencing a call to action concerning the development and implementation of sustainable chemical processes and transformations. 1 The development of base metal catalysts, in place of their precious metal counterparts, is one method to reduce both cost and toxicity while opening avenues for novel reactivity. 2 In recent years, pincer complexes have shown remarkable catalytic activity. 3 Iron, cobalt, and nickel hydride species featuring strongly trans -influencing, anionic central donor atoms (PCP, POCOP, PSiP, PBP) have been shown to rapidly insert CO 2 into the metal-hydride (M-H) bond later resulting in the formation of formate. 4 However, CO 2 activation by species without a M-H bond can be more challenging. Looking to take advantage of the secondary coordination sphere, recent research has focused on the inclusion of Lewis basic and acid moieties into the ligand periphery as a means to tailor reactivity. 5 For example cooperative reactivity between platinum and a peripheral aluminum atom has been shown to activate CO 2 . 6 Herein, we describe the synthesis of a series of PCP pincer ligands featuring Lewis acidic moieties (silyl or boryl) in the secondary coordination sphere. The formation of strong Si-O and B-O/N bonding interactions are leveraged to activate Lewis basic carbonyl substrates utilizing nickel. Insights into the sustainability and green chemistry considerations of the species described are provided. Herein, we describe the synthesis of a series of PCP pincer ligands featuring Lewis acidic moieties (silyl or boryl) in the secondary coordination sphere. The formation of strong Si-O and B-O/N bonding interactions are leveraged to activate Lewis basic carbonyl substrates utilizing nickel. Insights into the sustainability and green chemistry considerations of the species described are provided. activation by species without a M-H bond can be more challenging. Looking to take advantage of the secondary coordination sphere, recent research has focused on the inclusion of Lewis basic and acid moieties into the ligand periphery as a means to tailor reactivity. 5 For example cooperative reactivity between platinum and a peripheral aluminum atom has been shown to activate CO 2 . 6
(1) Matlin, S. A.; Cornell, S. E.; Krief, A.; Hopf, H.; Mehta, G. Chemical Science 2022 , 13 (40), 11710–11720. (2) Clapson, M. L.; Durfy, C. S.; Facchinato, D.; Drover, M. W. Cell Reports Physical Science 2023 , 4 (9), 101548. (3) van Koten , G.; Hollis, T. K.; Morales‐Morales, D. European Journal of Inorganic Chemistry 2020 , 2020 (47), 4416–4417. (4) Eberhardt, N. A.; Guan, H. Reduction of CO 2 Mediated or Catalyzed by Pincer Complexes. In Pincer Compounds ; Elsevier, 2018; pp 67–99. (5) Durfy, C. S.; Zurakowski, J. A.; Drover, M. W. ChemSusChem 2024 , 17 (13), e202400039. (6) Devillard, M.; Declercq, R.; Nicolas, E.; Ehlers, A. W.; Backs, J.; Saffon-Merceron, N.; Bouhadir, G.; Slootweg, J. C.; Uhl, W.; Bourissou, D. J Am Chem Soc 2016 , 138 (14), 4917–4926. References 1. Matlin, S. A.; Cornell, S. E.; Krief, A.; Hopf, H.; Mehta, G. Chemical Science 2022 , 13 (40), 11710–11720. 2. Clapson, M. L.; Durfy, C. S.; Facchinato, D.; Drover, M. W. Cell Reports Physical Science 2023 , 4 (9), 101548. 3. van Koten, G.; Hollis, T. K.; Morales–Morales, D. European Journal of Inorganic Chemistry 2020 , 2020 (47), 4416–4417. 4. Eberhardt, N. A.; Guan, H. Reduction of CO2 Mediated or Catalyzed by Pincer Complexes. In Pincer Compounds ; Elsevier, 2018; pp 67–99. 5. Durfy, C. S.; Zurakowski, J. A.; Drover, M. W. ChemSusChem 2024 , 17 (13), e202400039. 6. Devillard, M.; Declercq, R.; Nicolas, E.; Ehlers, A. W.; Backs, J.; Saffon-Merceron, N.; Bouhadir, G.; Slootweg, J. C.; Uhl, W.; Bourissou, D. J Am Chem Soc 2016 , 138 (14), 4917–4926.
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