Proton-Responsive Ligands Promote CO2 Capture and Accelerate Catalytic CO2/HCO2 – Interconversion
The synthesis and investigation of [Rh(DHMPE)2][BF4] (1) are reported. 1 features proton-responsive 1,2-bis[(dihydroxymethyl)phosphino]ethane (DHMPE) ligands, which readily capture CO2 from atmospheric sources upon deprotonation. The protonation state of the DHMPE ligand was observed to have a...
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Veröffentlicht in: | Inorganic chemistry 2024-10, Vol.63 (42), p.19527-19535 |
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creator | Barlow, Jeffrey M. Gupta, Nikita Glusac, Ksenija D. Tiede, David M. Kaphan, David M. |
description | The synthesis and investigation of [Rh(DHMPE)2][BF4] (1) are reported. 1 features proton-responsive 1,2-bis[(dihydroxymethyl)phosphino]ethane (DHMPE) ligands, which readily capture CO2 from atmospheric sources upon deprotonation. The protonation state of the DHMPE ligand was observed to have a significant impact on the catalytic reactivity of 1 with CO2. Deprotonation and CO2 binding to 1 result in a ∼10-fold rate enhancement in catalytic degenerate CO2 reduction with formate, monitored by 12C/13C isotope exchange between H12CO2 – and 13CO2. Studies performed using a similar complex lacking the hydroxyl ligand functionality ([Rh(DEPE)2][BF4] where DEPE = 1,2-bis(diethylphosphino)ethane) do not show the same rate enhancements when base is added. Based upon the cation-dependent activity of the catalyst, Eyring analysis, and cation sequestration experiments, CO2 binding to 1 is proposed to facilitate preorganization of formate/CO2 in the transition state via ligand-based encapsulation of Na+ or K+ cations to lower the activation energy and increase the observed catalytic rate. Incorporation of proton-responsive DHMPE ligands provides a unique approach to accelerate the kinetics of catalytic CO2 reduction to formate. |
doi_str_mv | 10.1021/acs.inorgchem.4c02092 |
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The protonation state of the DHMPE ligand was observed to have a significant impact on the catalytic reactivity of 1 with CO2. Deprotonation and CO2 binding to 1 result in a ∼10-fold rate enhancement in catalytic degenerate CO2 reduction with formate, monitored by 12C/13C isotope exchange between H12CO2 – and 13CO2. Studies performed using a similar complex lacking the hydroxyl ligand functionality ([Rh(DEPE)2][BF4] where DEPE = 1,2-bis(diethylphosphino)ethane) do not show the same rate enhancements when base is added. Based upon the cation-dependent activity of the catalyst, Eyring analysis, and cation sequestration experiments, CO2 binding to 1 is proposed to facilitate preorganization of formate/CO2 in the transition state via ligand-based encapsulation of Na+ or K+ cations to lower the activation energy and increase the observed catalytic rate. 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Based upon the cation-dependent activity of the catalyst, Eyring analysis, and cation sequestration experiments, CO2 binding to 1 is proposed to facilitate preorganization of formate/CO2 in the transition state via ligand-based encapsulation of Na+ or K+ cations to lower the activation energy and increase the observed catalytic rate. 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Chem</addtitle><date>2024-10-21</date><risdate>2024</risdate><volume>63</volume><issue>42</issue><spage>19527</spage><epage>19535</epage><pages>19527-19535</pages><issn>0020-1669</issn><issn>1520-510X</issn><eissn>1520-510X</eissn><abstract>The synthesis and investigation of [Rh(DHMPE)2][BF4] (1) are reported. 1 features proton-responsive 1,2-bis[(dihydroxymethyl)phosphino]ethane (DHMPE) ligands, which readily capture CO2 from atmospheric sources upon deprotonation. The protonation state of the DHMPE ligand was observed to have a significant impact on the catalytic reactivity of 1 with CO2. Deprotonation and CO2 binding to 1 result in a ∼10-fold rate enhancement in catalytic degenerate CO2 reduction with formate, monitored by 12C/13C isotope exchange between H12CO2 – and 13CO2. Studies performed using a similar complex lacking the hydroxyl ligand functionality ([Rh(DEPE)2][BF4] where DEPE = 1,2-bis(diethylphosphino)ethane) do not show the same rate enhancements when base is added. Based upon the cation-dependent activity of the catalyst, Eyring analysis, and cation sequestration experiments, CO2 binding to 1 is proposed to facilitate preorganization of formate/CO2 in the transition state via ligand-based encapsulation of Na+ or K+ cations to lower the activation energy and increase the observed catalytic rate. Incorporation of proton-responsive DHMPE ligands provides a unique approach to accelerate the kinetics of catalytic CO2 reduction to formate.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.inorgchem.4c02092</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-5293-7784</orcidid><orcidid>https://orcid.org/0000-0002-9536-8021</orcidid><orcidid>https://orcid.org/0000-0002-2784-4954</orcidid><orcidid>https://orcid.org/0000-0002-2734-057X</orcidid></addata></record> |
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title | Proton-Responsive Ligands Promote CO2 Capture and Accelerate Catalytic CO2/HCO2 – Interconversion |
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