ACS Organic & Inorganic Au最新文献_第4页

Applications of Antimony in Catalysis. 锑在催化中的应用。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-11-06 eCollection Date: 2025-02-05 DOI: 10.1021/acsorginorgau.4c00072

Lewen Wu, Choon-Hong Tan, Xinyi Ye

{"title":"Applications of Antimony in Catalysis.","authors":"Lewen Wu, Choon-Hong Tan, Xinyi Ye","doi":"10.1021/acsorginorgau.4c00072","DOIUrl":"10.1021/acsorginorgau.4c00072","url":null,"abstract":"Antimony is a fifth-period element in the nitrogen family, a silver-white metalloid with weak conductivity and thermal conductivity. It is stable at room temperature and does not react easily with oxygen and water in the air. Natural minerals are found in the form of sulfides. Current research and applications are mostly concentrated on material modification, utilizing the properties of antimony in traditional chemical industries, helping alloys improve their flame retardancy, stability, increasing semiconductor performance, etc. For example, to enhance the electronic conductivity, after coating or embedding antimony or its derivatives in thin layers in photonic nanomaterials, the performance of the original material in photoelectrochemical catalysis can be effectively increased, thereby expanding the efficiency of oxidation-reduction reactions accounting for the degradation of organic matter in wastewater. However, the catalytic reaction between the derivatives of antimony and organic compounds beside the material is less studied, and the mechanism of the studies in organic synthesis is relatively unclear. The reported organic synthesis related to antimony is mainly in the form of Lewis acid catalysts or dual-metal catalytic systems combined with other metals. This Review will focus on the application of antimony in photocatalysis, electrocatalysis, and other organic syntheses in the past 10 years.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"13-25"},"PeriodicalIF":3.3,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803468/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Applications of Antimony in Catalysis 锑在催化中的应用

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-11-06 DOI: 10.1021/acsorginorgau.4c0007210.1021/acsorginorgau.4c00072

Lewen Wu, Choon-Hong Tan* and Xinyi Ye*,

{"title":"Applications of Antimony in Catalysis","authors":"Lewen Wu, Choon-Hong Tan* and Xinyi Ye*, ","doi":"10.1021/acsorginorgau.4c0007210.1021/acsorginorgau.4c00072","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00072https://doi.org/10.1021/acsorginorgau.4c00072","url":null,"abstract":"Antimony is a fifth-period element in the nitrogen family, a silver-white metalloid with weak conductivity and thermal conductivity. It is stable at room temperature and does not react easily with oxygen and water in the air. Natural minerals are found in the form of sulfides. Current research and applications are mostly concentrated on material modification, utilizing the properties of antimony in traditional chemical industries, helping alloys improve their flame retardancy, stability, increasing semiconductor performance, etc. For example, to enhance the electronic conductivity, after coating or embedding antimony or its derivatives in thin layers in photonic nanomaterials, the performance of the original material in photoelectrochemical catalysis can be effectively increased, thereby expanding the efficiency of oxidation–reduction reactions accounting for the degradation of organic matter in wastewater. However, the catalytic reaction between the derivatives of antimony and organic compounds beside the material is less studied, and the mechanism of the studies in organic synthesis is relatively unclear. The reported organic synthesis related to antimony is mainly in the form of Lewis acid catalysts or dual-metal catalytic systems combined with other metals. This Review will focus on the application of antimony in photocatalysis, electrocatalysis, and other organic syntheses in the past 10 years.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"13–25 13–25"},"PeriodicalIF":3.3,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00072","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Crystal Chemistry and Design Principles of Altermagnets. 交替磁体的晶体化学和设计原理。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-23 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00064

Chao-Chun Wei, Erick Lawrence, Alyssa Tran, Huiwen Ji

{"title":"Crystal Chemistry and Design Principles of Altermagnets.","authors":"Chao-Chun Wei, Erick Lawrence, Alyssa Tran, Huiwen Ji","doi":"10.1021/acsorginorgau.4c00064","DOIUrl":"10.1021/acsorginorgau.4c00064","url":null,"abstract":"Altermagnetism was very recently identified as a new type of magnetic phase beyond the conventional dichotomy of ferromagnetism (FM) and antiferromagnetism (AFM). Its globally compensated magnetization and directional spin polarization promise new properties such as spin-polarized conductivity, spin-transfer torque, anomalous Hall effect, tunneling, and giant magnetoresistance that are highly useful for the next-generation memory devices, magnetic detectors, and energy conversion. Though this area has been historically led by the thin-film community, the identification of altermagnetism ultimately relies on precise magnetic structure determination, which can be most efficiently done in bulk materials. Our review, written from a materials chemistry perspective, intends to encourage materials and solid-state chemists to make contributions to this emerging topic through new materials discovery by leveraging neutron diffraction to determine the magnetic structures as well as bulk crystal growth for exploring exotic properties. We first review the symmetric classification for the identification of altermagnets with a summary of chemical principles and design rules, followed by a discussion of the unique physical properties in relation to crystal and magnetic structural symmetry. Several major families of compounds in which altermagnets have been identified are then reviewed. We conclude by giving an outlook for future directions.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"604-619"},"PeriodicalIF":3.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621956/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Crystal Chemistry and Design Principles of Altermagnets 交替磁体的晶体化学和设计原理

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-23 DOI: 10.1021/acsorginorgau.4c0006410.1021/acsorginorgau.4c00064

Chao-Chun Wei, Erick Lawrence, Alyssa Tran and Huiwen Ji*,

{"title":"Crystal Chemistry and Design Principles of Altermagnets","authors":"Chao-Chun Wei, Erick Lawrence, Alyssa Tran and Huiwen Ji*, ","doi":"10.1021/acsorginorgau.4c0006410.1021/acsorginorgau.4c00064","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00064https://doi.org/10.1021/acsorginorgau.4c00064","url":null,"abstract":"Altermagnetism was very recently identified as a new type of magnetic phase beyond the conventional dichotomy of ferromagnetism (FM) and antiferromagnetism (AFM). Its globally compensated magnetization and directional spin polarization promise new properties such as spin-polarized conductivity, spin-transfer torque, anomalous Hall effect, tunneling, and giant magnetoresistance that are highly useful for the next-generation memory devices, magnetic detectors, and energy conversion. Though this area has been historically led by the thin-film community, the identification of altermagnetism ultimately relies on precise magnetic structure determination, which can be most efficiently done in bulk materials. Our review, written from a materials chemistry perspective, intends to encourage materials and solid-state chemists to make contributions to this emerging topic through new materials discovery by leveraging neutron diffraction to determine the magnetic structures as well as bulk crystal growth for exploring exotic properties. We first review the symmetric classification for the identification of altermagnets with a summary of chemical principles and design rules, followed by a discussion of the unique physical properties in relation to crystal and magnetic structural symmetry. Several major families of compounds in which altermagnets have been identified are then reviewed. We conclude by giving an outlook for future directions.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"604–619 604–619"},"PeriodicalIF":3.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00064","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride 第一行过渡金属二氧化碳还原电催化剂在氯化苄电化学羧化反应中的应用

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-20 DOI: 10.1021/acsorginorgau.4c0005110.1021/acsorginorgau.4c00051

Pornwimon Kongkiatkrai, Thana Anusanti and Teera Chantarojsiri*,

{"title":"Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride","authors":"Pornwimon Kongkiatkrai, Thana Anusanti and Teera Chantarojsiri*, ","doi":"10.1021/acsorginorgau.4c0005110.1021/acsorginorgau.4c00051","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00051https://doi.org/10.1021/acsorginorgau.4c00051","url":null,"abstract":"Carbon dioxide (CO2) is an abundant and useful C1 feedstock for electrocarboxylation, a process that incorporates a carboxyl moiety into an organic molecule. In this work, three first-row transition metal CO2 reduction electrocatalysts, NiPDIiPr (1), NiTPA (2), and Fe(salenCl4) (3), were explored as electrocarboxylation catalysts with benzyl chloride as a substrate. The cyclic voltammograms of all three catalysts showed current enhancements in the presence of benzyl chloride under a CO2 atmosphere. Introduction of DMAP as additives showed further current enhancement. Electrolyses with one-compartment cell generated a moderate yield of phenylacetic acid. Addition of MgBr2 was proven to be crucial to the formation of the carboxylate product. While the yield of carboxylation was moderate, this work showed an example of electrocarboxylation of benzyl chloride without using a metal electrode or sacrificial anode, which could lead to a more sustainable carboxylation methodology.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"620–627 620–627"},"PeriodicalIF":3.3,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00051","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride. 第一行过渡金属二氧化碳还原电催化剂在氯化苄电化学羧化反应中的应用。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-20 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00051

Pornwimon Kongkiatkrai, Thana Anusanti, Teera Chantarojsiri

{"title":"Repurposing First-Row Transition Metal Carbon Dioxide Reduction Electrocatalysts for Electrochemical Carboxylation of Benzyl Chloride.","authors":"Pornwimon Kongkiatkrai, Thana Anusanti, Teera Chantarojsiri","doi":"10.1021/acsorginorgau.4c00051","DOIUrl":"10.1021/acsorginorgau.4c00051","url":null,"abstract":"Carbon dioxide (CO2) is an abundant and useful C1 feedstock for electrocarboxylation, a process that incorporates a carboxyl moiety into an organic molecule. In this work, three first-row transition metal CO2 reduction electrocatalysts, NiPDIiPr (1), NiTPA (2), and Fe(salenCl4) (3), were explored as electrocarboxylation catalysts with benzyl chloride as a substrate. The cyclic voltammograms of all three catalysts showed current enhancements in the presence of benzyl chloride under a CO2 atmosphere. Introduction of DMAP as additives showed further current enhancement. Electrolyses with one-compartment cell generated a moderate yield of phenylacetic acid. Addition of MgBr2 was proven to be crucial to the formation of the carboxylate product. While the yield of carboxylation was moderate, this work showed an example of electrocarboxylation of benzyl chloride without using a metal electrode or sacrificial anode, which could lead to a more sustainable carboxylation methodology.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"620-627"},"PeriodicalIF":3.3,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621952/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO₂ by Bipyridine Complexes Bearing Pendant Amines: A DFT Study. 含垂胺联吡啶配合物电催化还原CO2的金属依赖机理：DFT研究。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-11 eCollection Date: 2025-02-05 DOI: 10.1021/acsorginorgau.4c00046

Mahika Luthra, Abril C Castro, David Balcells, Kim Daasbjerg, Ainara Nova

{"title":"Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study.","authors":"Mahika Luthra, Abril C Castro, David Balcells, Kim Daasbjerg, Ainara Nova","doi":"10.1021/acsorginorgau.4c00046","DOIUrl":"10.1021/acsorginorgau.4c00046","url":null,"abstract":"In this study, the electrocatalytic reduction of carbon dioxide by MnI, ReI, and RuII bipyridine complexes bearing pendant amines is evaluated by DFT methods. Prior experimental studies showed that introducing pendant amines in the secondary coordination sphere of the catalyst shifts product selectivity from CO to HCOO- (in the presence of a proton source) in the case of Mn. In contrast, CO is the major product with Re and Ru. This work includes a comprehensive study of the pathways leading to CO, HCOO-, and H2 to elucidate the energetic preferences that underlie product selectivity. Our results show that switching the metal center leads to changes in the preferred mechanism. While with Mn, the reaction is preferred in an endo configuration, allowing the participation of amines in the hydride formation, reactivity on the exo configuration is preferred with Re. In addition, the distinct redox properties of Re allow for the formation of Re OCOCO2-bridged adducts that lead to CO without a proton source. Further, the ability of Ru to exchange the two Cl- anions changes the preferred coordination number of Ru compared to Mn and Re and, consequently, its reaction mechanism. Overall, this study provides the structure and reactivity insight needed for further catalyst design.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"26-36"},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803466/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study 含垂胺联吡啶配合物电催化还原CO2的金属依赖机理：DFT研究

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-11 DOI: 10.1021/acsorginorgau.4c0004610.1021/acsorginorgau.4c00046

Mahika Luthra, Abril C. Castro*, David Balcells, Kim Daasbjerg and Ainara Nova*,

{"title":"Metal-Dependent Mechanism of the Electrocatalytic Reduction of CO2 by Bipyridine Complexes Bearing Pendant Amines: A DFT Study","authors":"Mahika Luthra, Abril C. Castro*, David Balcells, Kim Daasbjerg and Ainara Nova*, ","doi":"10.1021/acsorginorgau.4c0004610.1021/acsorginorgau.4c00046","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00046https://doi.org/10.1021/acsorginorgau.4c00046","url":null,"abstract":"In this study, the electrocatalytic reduction of carbon dioxide by MnI, ReI, and RuII bipyridine complexes bearing pendant amines is evaluated by DFT methods. Prior experimental studies showed that introducing pendant amines in the secondary coordination sphere of the catalyst shifts product selectivity from CO to HCOO– (in the presence of a proton source) in the case of Mn. In contrast, CO is the major product with Re and Ru. This work includes a comprehensive study of the pathways leading to CO, HCOO–, and H2 to elucidate the energetic preferences that underlie product selectivity. Our results show that switching the metal center leads to changes in the preferred mechanism. While with Mn, the reaction is preferred in an endo configuration, allowing the participation of amines in the hydride formation, reactivity on the exo configuration is preferred with Re. In addition, the distinct redox properties of Re allow for the formation of Re OCOCO2-bridged adducts that lead to CO without a proton source. Further, the ability of Ru to exchange the two Cl– anions changes the preferred coordination number of Ru compared to Mn and Re and, consequently, its reaction mechanism. Overall, this study provides the structure and reactivity insight needed for further catalyst design.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"26–36 26–36"},"PeriodicalIF":3.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2 催化剂质子化改变了电化学氢化物向CO2转移的机理

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-04 DOI: 10.1021/acsorginorgau.4c0004110.1021/acsorginorgau.4c00041

Kevin Y. C. Lee, Dmitry E. Polyansky, David C. Grills, James C. Fettinger, Marcos Aceves and Louise A. Berben*,

{"title":"Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2","authors":"Kevin Y. C. Lee, Dmitry E. Polyansky, David C. Grills, James C. Fettinger, Marcos Aceves and Louise A. Berben*, ","doi":"10.1021/acsorginorgau.4c0004110.1021/acsorginorgau.4c00041","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00041https://doi.org/10.1021/acsorginorgau.4c00041","url":null,"abstract":"It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemically driven hydride transfer (HT) catalysis. Protonated, air-stable [HFe4N(triethyl phosphine (PEt3))4(CO)8] (H4) was synthesized by reaction of PEt3 with [Fe4N(CO)12]− (A–) in tetrahydrofuran, with addition of benzoic acid to the reaction mixture. The reduction potential of H4 is −1.70 V vs SCE which is 350 mV anodic of the reduction potential for 4–. Reactivity studies are consistent with HT to CO2 or to H+ (carbonic acid), as the chemical event following ET, when the electrocatalysis is performed under 1 atm of CO2 or N2, respectively. Taken together, the chemical and electrochemical studies of mechanism suggest an ECEC mechanism for the reduction of CO2 to formate or H+ to H2, promoted by H4. This stands in contrast to an ET, two chemical steps, followed by an ET (ECCE) mechanism that is promoted by the less electron rich catalyst A–, since A– must be reduced to A2– before HA– can be accessed.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"649–657 649–657"},"PeriodicalIF":3.3,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO₂. 催化剂质子化改变了电化学氢化物向CO2转移的机理。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-04 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00041

Kevin Y C Lee, Dmitry E Polyansky, David C Grills, James C Fettinger, Marcos Aceves, Louise A Berben

{"title":"Catalyst Protonation Changes the Mechanism of Electrochemical Hydride Transfer to CO2.","authors":"Kevin Y C Lee, Dmitry E Polyansky, David C Grills, James C Fettinger, Marcos Aceves, Louise A Berben","doi":"10.1021/acsorginorgau.4c00041","DOIUrl":"10.1021/acsorginorgau.4c00041","url":null,"abstract":"It is well-known that addition of a cationic functional group to a molecule lowers the necessary applied potential for an electron transfer (ET) event. This report studies the effect of a proton (a cation) on the mechanism of electrochemically driven hydride transfer (HT) catalysis. Protonated, air-stable [HFe4N(triethyl phosphine (PEt3))4(CO)8] (H4) was synthesized by reaction of PEt3 with [Fe4N(CO)12]- (A -) in tetrahydrofuran, with addition of benzoic acid to the reaction mixture. The reduction potential of H4 is -1.70 V vs SCE which is 350 mV anodic of the reduction potential for 4 -. Reactivity studies are consistent with HT to CO2 or to H+ (carbonic acid), as the chemical event following ET, when the electrocatalysis is performed under 1 atm of CO2 or N2, respectively. Taken together, the chemical and electrochemical studies of mechanism suggest an ECEC mechanism for the reduction of CO2 to formate or H+ to H2, promoted by H4. This stands in contrast to an ET, two chemical steps, followed by an ET (ECCE) mechanism that is promoted by the less electron rich catalyst A -, since A - must be reduced to A 2- before HA - can be accessed.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"649-657"},"PeriodicalIF":3.3,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621949/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0