ACS Organic & Inorganic Au最新文献_第2页

Modified Working Electrodes for Organic Electrosynthesis. 用于有机电合成的改良工作电极。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-02 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00050

Alexander C Reidell, Kristen E Pazder, Christopher T LeBarron, Skylar A Stewart, Seyyedamirhossein Hosseini

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引用次数: 0

Modified Working Electrodes for Organic Electrosynthesis 用于有机电合成的改良工作电极

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-02 DOI: 10.1021/acsorginorgau.4c0005010.1021/acsorginorgau.4c00050

Alexander C. Reidell, Kristen E. Pazder, Christopher T. LeBarron, Skylar A. Stewart and Seyyedamirhossein Hosseini*,

{"title":"Modified Working Electrodes for Organic Electrosynthesis","authors":"Alexander C. Reidell, Kristen E. Pazder, Christopher T. LeBarron, Skylar A. Stewart and Seyyedamirhossein Hosseini*, ","doi":"10.1021/acsorginorgau.4c0005010.1021/acsorginorgau.4c00050","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00050https://doi.org/10.1021/acsorginorgau.4c00050","url":null,"abstract":"Organic electrosynthesis has gained much attention over the last few decades as a promising alternative to traditional synthesis methods. Electrochemical approaches offer numerous advantages over traditional organic synthesis procedures. One of the most interesting aspects of electroorganic synthesis is the ability to tune many parameters to affect the outcome of the reaction of interest. One such parameter is the composition of the working electrode. By changing the electrode material, one can influence the selectivity, product distribution, and rate of organic reactions. In this Review, we describe several electrode materials and modifications with applications in organic electrosynthetic transformations. Included in this discussion are modifications of electrodes with nanoparticles, composite materials, polymers, organic frameworks, and surface-bound mediators. We first discuss the important physicochemical and electrochemical properties of each material. Then, we briefly summarize several relevant examples of each class of electrodes, with the goal of providing readers with a catalog of electrode materials for a wide variety of organic syntheses.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"579–603 579–603"},"PeriodicalIF":3.3,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761038","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

Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring. 扩展五氟苯基n -杂化卟啉的化学性质：反吡咯环外3-C位置的二酮酸取代和衍生化。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-10-01 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00065

Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw, Chen-Hsiung Hung

{"title":"Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring.","authors":"Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw, Chen-Hsiung Hung","doi":"10.1021/acsorginorgau.4c00065","DOIUrl":"10.1021/acsorginorgau.4c00065","url":null,"abstract":"In this study, we synthesized two new 3-C-substituted pentafluorophenyl-N-confused porphyrins (PFNCPs), one with acetylacetonate (PFNCP-acac, 2a) and the other with ylidene-2-propanone (PFNCP-ac, 3a), through a one-pot reaction in the absence of a catalyst. Under mild acidic and heating conditions, the acac-substituted compound underwent acyl cleavage degradation, yielding ac-substituted product 3a. Subsequent chelation of the acac-substituted PFNCP with BF2 resulted in a boron diketonate derivative, PFNCP-acacBF2 (4). Additionally, an electrocyclic reaction of the ac-substituted PFNCP 3a, without a catalyst, produced a tricyclic fused [6,6,5]-TF-PFNCP (5). This tricyclic product could also be obtained directly from PFNCP-acac 2a under heating conditions. The absorption spectra revealed that acac- and ac-substituted macrocycles exhibit either a single or split Soret band, respectively, in the 400-550 nm range, along with multiple Q bands spanning the 580-690 nm region. While BF2 derivatization caused a slight red shift in the absorption spectra, the [6,6,5]-tricyclic fused NCP demonstrated a significant red shift. All newly synthesized compounds were characterized by using single-crystal X-ray structures, 1H NMR spectroscopy, and mass spectrometry. Density functional theory (DFT) studies were conducted to elucidate the photophysical properties of these macrocycles.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"681-691"},"PeriodicalIF":3.3,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621957/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802375","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

Study of the BHT Oxidation Mechanism Coupling Theory and Experiment. BHT氧化机理耦合理论与实验研究。

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-30 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00067

Edgardo Maximiliano Gavilán-Arriazu, Rubén Darío Alaniz, Patcharawat Charoen-Amornkitt, Juan Manuel Fernández, Gastón Darío Pierini, Sergio Antonio Rodriguez

{"title":"Study of the BHT Oxidation Mechanism Coupling Theory and Experiment.","authors":"Edgardo Maximiliano Gavilán-Arriazu, Rubén Darío Alaniz, Patcharawat Charoen-Amornkitt, Juan Manuel Fernández, Gastón Darío Pierini, Sergio Antonio Rodriguez","doi":"10.1021/acsorginorgau.4c00067","DOIUrl":"10.1021/acsorginorgau.4c00067","url":null,"abstract":"In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pK a and standard oxidation potential (E ox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"692-704"},"PeriodicalIF":3.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621955/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802412","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

Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring 扩展五氟苯基n -杂化卟啉的化学性质：反吡咯环外3-C位置的二酮酸取代和衍生化

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-30 DOI: 10.1021/acsorginorgau.4c0006510.1021/acsorginorgau.4c00065

Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw* and Chen-Hsiung Hung*,

{"title":"Expanding the Chemistry of Pentafluorophenyl-N-Confused Porphyrin: Diketonate Substitution and Derivatizations at the External 3-C Position of the Inverted Pyrrole Ring","authors":"Bhakyaraj Kasi, Belarani Ojha, Wen-Feng Liaw* and Chen-Hsiung Hung*, ","doi":"10.1021/acsorginorgau.4c0006510.1021/acsorginorgau.4c00065","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00065https://doi.org/10.1021/acsorginorgau.4c00065","url":null,"abstract":"In this study, we synthesized two new 3-C-substituted pentafluorophenyl-N-confused porphyrins (PFNCPs), one with acetylacetonate (PFNCP-acac, 2a) and the other with ylidene-2-propanone (PFNCP-ac, 3a), through a one-pot reaction in the absence of a catalyst. Under mild acidic and heating conditions, the acac-substituted compound underwent acyl cleavage degradation, yielding ac-substituted product 3a. Subsequent chelation of the acac-substituted PFNCP with BF2 resulted in a boron diketonate derivative, PFNCP-acacBF2 (4). Additionally, an electrocyclic reaction of the ac-substituted PFNCP 3a, without a catalyst, produced a tricyclic fused [6,6,5]-TF-PFNCP (5). This tricyclic product could also be obtained directly from PFNCP-acac 2a under heating conditions. The absorption spectra revealed that acac- and ac-substituted macrocycles exhibit either a single or split Soret band, respectively, in the 400–550 nm range, along with multiple Q bands spanning the 580–690 nm region. While BF2 derivatization caused a slight red shift in the absorption spectra, the [6,6,5]-tricyclic fused NCP demonstrated a significant red shift. All newly synthesized compounds were characterized by using single-crystal X-ray structures, 1H NMR spectroscopy, and mass spectrometry. Density functional theory (DFT) studies were conducted to elucidate the photophysical properties of these macrocycles.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"681–691 681–691"},"PeriodicalIF":3.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00065","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760847","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

Study of the BHT Oxidation Mechanism Coupling Theory and Experiment BHT氧化机理耦合理论与实验研究

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-29 DOI: 10.1021/acsorginorgau.4c0006710.1021/acsorginorgau.4c00067

Edgardo Maximiliano Gavilán-Arriazu*, Rubén Darío Alaniz, Patcharawat Charoen-amornkitt, Juan Manuel Fernández, Gastón Darío Pierini and Sergio Antonio Rodriguez*,

{"title":"Study of the BHT Oxidation Mechanism Coupling Theory and Experiment","authors":"Edgardo Maximiliano Gavilán-Arriazu*, Rubén Darío Alaniz, Patcharawat Charoen-amornkitt, Juan Manuel Fernández, Gastón Darío Pierini and Sergio Antonio Rodriguez*, ","doi":"10.1021/acsorginorgau.4c0006710.1021/acsorginorgau.4c00067","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00067https://doi.org/10.1021/acsorginorgau.4c00067","url":null,"abstract":"In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"692–704 692–704"},"PeriodicalIF":3.3,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00067","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761385","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

Copper-Mediated -CF(OCF₃)(CF₂H) Transfer to Organic Electrophiles. 铜介导的-CF(OCF3)（CF2H）向有机亲电试剂的转移

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-20 eCollection Date: 2024-12-04 DOI: 10.1021/acsorginorgau.4c00038

Behnaz Ghaffari, Luana L T N Porto, Nicole Johnson, Jeffrey S Ovens, Christian Ehm, R Tom Baker

{"title":"Copper-Mediated -CF(OCF3)(CF2H) Transfer to Organic Electrophiles.","authors":"Behnaz Ghaffari, Luana L T N Porto, Nicole Johnson, Jeffrey S Ovens, Christian Ehm, R Tom Baker","doi":"10.1021/acsorginorgau.4c00038","DOIUrl":"10.1021/acsorginorgau.4c00038","url":null,"abstract":"The integration of fluorine into medicinal compounds has become a widely used strategy to improve the biochemical and therapeutic properties of drugs. Inclusion of -CF2H and -OCF3 fluoroalkyl groups has garnered attention due to their bioisosteric properties, enhanced lipophilicity, and potential hydrogen-bonding capability in bioactive substances. In this study, we prepared a series of stable Cu[CF(OCF3)(CF2H)]L n complexes by insertion of commercially available perfluoro(methyl vinyl ether), CF2=CF(OCF3), into Cu-H bonds derived from Stryker's reagent, [CuH(PPh3)]6, using ancillary ligands L. Notably, certain of these complexes effectively transfer the fluoroalkyl group to aroyl chlorides. Through reaction optimization and computational analysis, we identified dimethylsulfoxide as a pivotal coligand, playing a distinctive role in enabling the fluoroalkylation of a range of aroyl chlorides and aryl iodides. The latter also benefits from addition of CuBr to abstract PPh3, generating solvent-stabilized Cu[CF(OCF3)(CF2H)]. These methodologies allow for the introduction of geminal -OCF3 and -CF2H groups in a single transformation.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"628-639"},"PeriodicalIF":3.3,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11621958/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142802373","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

Copper-Mediated −CF(OCF3)(CF2H) Transfer to Organic Electrophiles 铜介导的−CF(OCF3)（CF2H）向有机亲电试剂的转移

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-20 DOI: 10.1021/acsorginorgau.4c0003810.1021/acsorginorgau.4c00038

Behnaz Ghaffari, Luana L. T. N. Porto, Nicole Johnson, Jeffrey S. Ovens, Christian Ehm* and R. Tom Baker*,

{"title":"Copper-Mediated −CF(OCF3)(CF2H) Transfer to Organic Electrophiles","authors":"Behnaz Ghaffari, Luana L. T. N. Porto, Nicole Johnson, Jeffrey S. Ovens, Christian Ehm* and R. Tom Baker*, ","doi":"10.1021/acsorginorgau.4c0003810.1021/acsorginorgau.4c00038","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00038https://doi.org/10.1021/acsorginorgau.4c00038","url":null,"abstract":"The integration of fluorine into medicinal compounds has become a widely used strategy to improve the biochemical and therapeutic properties of drugs. Inclusion of −CF2H and −OCF3 fluoroalkyl groups has garnered attention due to their bioisosteric properties, enhanced lipophilicity, and potential hydrogen-bonding capability in bioactive substances. In this study, we prepared a series of stable Cu[CF(OCF3)(CF2H)]Ln complexes by insertion of commercially available perfluoro(methyl vinyl ether), CF2═CF(OCF3), into Cu–H bonds derived from Stryker’s reagent, [CuH(PPh3)]6, using ancillary ligands L. Notably, certain of these complexes effectively transfer the fluoroalkyl group to aroyl chlorides. Through reaction optimization and computational analysis, we identified dimethylsulfoxide as a pivotal coligand, playing a distinctive role in enabling the fluoroalkylation of a range of aroyl chlorides and aryl iodides. The latter also benefits from addition of CuBr to abstract PPh3, generating solvent-stabilized Cu[CF(OCF3)(CF2H)]. These methodologies allow for the introduction of geminal −OCF3 and −CF2H groups in a single transformation.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"628–639 628–639"},"PeriodicalIF":3.3,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761266","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

Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes 揭示赤道异构体取代的非血红素铁络合物中的亚氯酸盐氧化途径

ACS Organic & Inorganic Au Pub Date : 2024-09-20 DOI: 10.1021/acsorginorgau.4c00045

Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser

{"title":"Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes","authors":"Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser","doi":"10.1021/acsorginorgau.4c00045","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00045","url":null,"abstract":"The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe2, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"202 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes 揭示等温杂原子取代非血红素铁配合物中绿泥石氧化途径

IF 3.3

ACS Organic & Inorganic Au Pub Date : 2024-09-20 DOI: 10.1021/acsorginorgau.4c0004510.1021/acsorginorgau.4c00045

Limashree Sahoo, Payal Panwar, Chivukula V. Sastri* and Sam P. de Visser*,

{"title":"Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes","authors":"Limashree Sahoo, Payal Panwar, Chivukula V. Sastri* and Sam P. de Visser*, ","doi":"10.1021/acsorginorgau.4c0004510.1021/acsorginorgau.4c00045","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00045https://doi.org/10.1021/acsorginorgau.4c00045","url":null,"abstract":"The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe2, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"4 6","pages":"673–680 673–680"},"PeriodicalIF":3.3,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00045","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142761254","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