Pub Date : 2020-10-28DOI: 10.1039/9781839160882-00012
Jose A. Silva, M. F. C. G. Silva, Manas Sutradhar, A. Pombeiro
Amavadin is a vanadium metallobiomolecule present in a few fungi Amanita that exhibits an unusual structure and coordination chemistry. This non-oxido-metal complex bears two particular N-oxyiminodicarboxylate ligands with single coordination bonds from all the eight donor atoms to the metal centre. Its biological role is yet unknown, although it mediates water oxidation and displays nitrite reductase-, catalase- and peroxidase-type activity, the latter on some thiols (including biological ones). Amavadin and its models can also catalyse peroxidative oxidation, peroxidative halogenation and carboxylation of alkanes and other hydrocarbons, as well as oxidation of alcohols, although under unlikely biological conditions. All these topics are addressed in this chapter.
{"title":"Chapter 2. Amavadin and Related Complexes as Oxidation Catalysts","authors":"Jose A. Silva, M. F. C. G. Silva, Manas Sutradhar, A. Pombeiro","doi":"10.1039/9781839160882-00012","DOIUrl":"https://doi.org/10.1039/9781839160882-00012","url":null,"abstract":"Amavadin is a vanadium metallobiomolecule present in a few fungi Amanita that exhibits an unusual structure and coordination chemistry. This non-oxido-metal complex bears two particular N-oxyiminodicarboxylate ligands with single coordination bonds from all the eight donor atoms to the metal centre. Its biological role is yet unknown, although it mediates water oxidation and displays nitrite reductase-, catalase- and peroxidase-type activity, the latter on some thiols (including biological ones). Amavadin and its models can also catalyse peroxidative oxidation, peroxidative halogenation and carboxylation of alkanes and other hydrocarbons, as well as oxidation of alcohols, although under unlikely biological conditions. All these topics are addressed in this chapter.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2020-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79360724","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}
{"title":"Catalysis with Earth-abundant Elements","authors":"Louise A. Berben","doi":"10.1039/9781788012775","DOIUrl":"https://doi.org/10.1039/9781788012775","url":null,"abstract":"","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2020-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78676433","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00479
L. Kustov, V. Isaeva
The concept of using hybrids of metal–organic frameworks (MOFs) with encapsulated structures, such as calixarenes, crown ethers, phthalocyanines and porphyrins, as nano-reactors or nano-containers for specific catalytic reactions is considered from the point of view of noncovalent interactions and molecular confinement in the porous architecture of MOFs of different structural types. Materials of this kind can be called “Russian matryoshka-type metal organic frameworks.” Controlling such interactions provides a key to enhancement of the efficiency of the catalysts and performance of adsorbents. The design of “green” and robust MOFs is of prime importance.
{"title":"CHAPTER 22. Hybrids of Metal–Organic Frameworks as Organized Supramolecular Nano-reactors","authors":"L. Kustov, V. Isaeva","doi":"10.1039/9781788016490-00479","DOIUrl":"https://doi.org/10.1039/9781788016490-00479","url":null,"abstract":"The concept of using hybrids of metal–organic frameworks (MOFs) with encapsulated structures, such as calixarenes, crown ethers, phthalocyanines and porphyrins, as nano-reactors or nano-containers for specific catalytic reactions is considered from the point of view of noncovalent interactions and molecular confinement in the porous architecture of MOFs of different structural types. Materials of this kind can be called “Russian matryoshka-type metal organic frameworks.” Controlling such interactions provides a key to enhancement of the efficiency of the catalysts and performance of adsorbents. The design of “green” and robust MOFs is of prime importance.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73653513","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00350
P. Hunt
Ionic liquids (ILs) exhibit a wide range of noncovalent (NC) interactions, coulombic, van der Waals, H-bonding, halogen bonding and π interactions, giving rise to polar, lipophilic and fluorous domains. ILs also exhibit a variety of unique features and a high level of complexity in a single liquid environment. In this chapter, an understanding of the underlying NC interactions within ILs is developed. Catalysis in ILs is a well-established and diverse field, the IL normally playing the role of solvent, but the IL can also be an additive or the catalyst. The prevalence of NC interactions within ILs leads to NC interactions playing an important role in catalytic mechanisms and reactivity. Selected cases from the literature are used to highlight specific examples. However, in many cases the focus of reports on catalysis in ILs is on the performance and products and not on the mechanistic details. The range of interactions possible can make unravelling the effect of an IL on a reaction very difficult. The purpose of this chapter is to build a robust understanding of the NC interactions that occur between catalyst and IL, with the aim of being better able to conceptualize a potential mechanism.
{"title":"CHAPTER 16. Noncovalent Interactions in Ionic Liquids","authors":"P. Hunt","doi":"10.1039/9781788016490-00350","DOIUrl":"https://doi.org/10.1039/9781788016490-00350","url":null,"abstract":"Ionic liquids (ILs) exhibit a wide range of noncovalent (NC) interactions, coulombic, van der Waals, H-bonding, halogen bonding and π interactions, giving rise to polar, lipophilic and fluorous domains. ILs also exhibit a variety of unique features and a high level of complexity in a single liquid environment. In this chapter, an understanding of the underlying NC interactions within ILs is developed. Catalysis in ILs is a well-established and diverse field, the IL normally playing the role of solvent, but the IL can also be an additive or the catalyst. The prevalence of NC interactions within ILs leads to NC interactions playing an important role in catalytic mechanisms and reactivity. Selected cases from the literature are used to highlight specific examples. However, in many cases the focus of reports on catalysis in ILs is on the performance and products and not on the mechanistic details. The range of interactions possible can make unravelling the effect of an IL on a reaction very difficult. The purpose of this chapter is to build a robust understanding of the NC interactions that occur between catalyst and IL, with the aim of being better able to conceptualize a potential mechanism.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74112331","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00168
Vijay S. Koshti, Samir H. Chikkali
This chapter summarizes the fundamentals of hydrogenation and hydroformylation reactions. An overview of state-of-the-art developments is presented to set the context. Subsequently, the significance of noncovalent interactions in these reactions is discussed in detail. Hydrogen bonding has been one of the leading noncovalent interactions that has been very frequently used in catalysis, including hydrogenation and hydroformylation reactions. Recent examples from the literature are presented to illustrate the role of hydrogen bonding in hydrogenation and hydroformylation. The impact of hydrogen bonding on catalyst development through self-assembly and the role of hydrogen bonding in directing a substrate to achieve high enantiomeric excess are discussed.
{"title":"CHAPTER 8. Noncovalent Interactions in Hydrogenation and Hydroformylation","authors":"Vijay S. Koshti, Samir H. Chikkali","doi":"10.1039/9781788016490-00168","DOIUrl":"https://doi.org/10.1039/9781788016490-00168","url":null,"abstract":"This chapter summarizes the fundamentals of hydrogenation and hydroformylation reactions. An overview of state-of-the-art developments is presented to set the context. Subsequently, the significance of noncovalent interactions in these reactions is discussed in detail. Hydrogen bonding has been one of the leading noncovalent interactions that has been very frequently used in catalysis, including hydrogenation and hydroformylation reactions. Recent examples from the literature are presented to illustrate the role of hydrogen bonding in hydrogenation and hydroformylation. The impact of hydrogen bonding on catalyst development through self-assembly and the role of hydrogen bonding in directing a substrate to achieve high enantiomeric excess are discussed.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83880611","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00001
K. Mahmudov, A. Gurbanov, M. F. C. G. Silva, A. Pombeiro
Over the past few decades, direct functionalization/activation of the C–H bond to C–E (E = C, N, O, S, metal, etc.) bonds has become one of the most valuable and straightforward protocols in modern synthetic chemistry. In parallel, controlling the selectivity remains a central challenge in the catalytic functionalization/activation of C–H bond(s) owing to the subtle differences in the reactivity of the various C–H bonds within the molecule. In this chapter, we discuss the crucial role of noncovalent interactions in C–H bond functionalization in alkanes, alkenes, alkynes, aromatics, heterocyclics, aldehydes and ketones. These weak forces can be powerful tools in the formation/stabilization of intermediates and in controlling the selectivity and outcome of a reaction.
在过去的几十年里，将C - h键直接功能化/激活为C - E (E = C, N, O, S，金属等)键已成为现代合成化学中最有价值和最直接的方法之一。同时，由于分子内各种碳氢键的反应性存在细微差异，控制碳氢键的选择性仍然是碳氢键催化功能化/活化的核心挑战。在本章中，我们讨论了非共价相互作用在烷烃、烯烃、炔烃、芳烃、杂环化合物、醛类和酮类化合物的C-H键功能化中的关键作用。这些弱力在中间体的形成/稳定以及控制反应的选择性和结果方面是强有力的工具。
{"title":"CHAPTER 1. Noncovalent Interactions in C–H Bond Functionalization","authors":"K. Mahmudov, A. Gurbanov, M. F. C. G. Silva, A. Pombeiro","doi":"10.1039/9781788016490-00001","DOIUrl":"https://doi.org/10.1039/9781788016490-00001","url":null,"abstract":"Over the past few decades, direct functionalization/activation of the C–H bond to C–E (E = C, N, O, S, metal, etc.) bonds has become one of the most valuable and straightforward protocols in modern synthetic chemistry. In parallel, controlling the selectivity remains a central challenge in the catalytic functionalization/activation of C–H bond(s) owing to the subtle differences in the reactivity of the various C–H bonds within the molecule. In this chapter, we discuss the crucial role of noncovalent interactions in C–H bond functionalization in alkanes, alkenes, alkynes, aromatics, heterocyclics, aldehydes and ketones. These weak forces can be powerful tools in the formation/stabilization of intermediates and in controlling the selectivity and outcome of a reaction.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91394170","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00455
Li Zhang, Jiewei Liu, C. Su
Metal–organic frameworks (MOFs) are promising candidates for CO2 capture and conversion as they possess remarkable properties, including large surface area, open channels and permanent porosity. Through the judicious selection of metal clusters and organic linkers, a framework with a desired topology can be realized. Furthermore, the study of the noncovalent interactions in MOFs provides significant insights into the relationship between the catalytic performance and the framework structure, which will also further promote the development of MOFs as heterogeneous catalysts for CO2 capture and conversion. This chapter is divided into four sections. The first section gives a brief introduction to the structures and chemical features of MOFs. The second section concentrates on MOFs as heterogeneous catalysts for the chemical fixation of CO2 with organic compounds. The third section presents MOFs as photocatalysts for CO2 reduction. The last section covers the application of MOFs in the electrocatalytic reduction of CO2. Particular challenges in the rational design and application of MOF catalysts and research opportunities for further development are highlighted. It is hoped that this chapter will not only serve as a starting point to gain insights into this challenging field but will also stimulate more intensive research on the development of creative MOFs as heterogeneous catalysts towards CO2 capture and conversion.
{"title":"CHAPTER 21. Application of Metal–Organic Frameworks in CO2 Capture and Conversion","authors":"Li Zhang, Jiewei Liu, C. Su","doi":"10.1039/9781788016490-00455","DOIUrl":"https://doi.org/10.1039/9781788016490-00455","url":null,"abstract":"Metal–organic frameworks (MOFs) are promising candidates for CO2 capture and conversion as they possess remarkable properties, including large surface area, open channels and permanent porosity. Through the judicious selection of metal clusters and organic linkers, a framework with a desired topology can be realized. Furthermore, the study of the noncovalent interactions in MOFs provides significant insights into the relationship between the catalytic performance and the framework structure, which will also further promote the development of MOFs as heterogeneous catalysts for CO2 capture and conversion. This chapter is divided into four sections. The first section gives a brief introduction to the structures and chemical features of MOFs. The second section concentrates on MOFs as heterogeneous catalysts for the chemical fixation of CO2 with organic compounds. The third section presents MOFs as photocatalysts for CO2 reduction. The last section covers the application of MOFs in the electrocatalytic reduction of CO2. Particular challenges in the rational design and application of MOF catalysts and research opportunities for further development are highlighted. It is hoped that this chapter will not only serve as a starting point to gain insights into this challenging field but will also stimulate more intensive research on the development of creative MOFs as heterogeneous catalysts towards CO2 capture and conversion.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75647546","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00026
S. Arimitsu, M. Higashi
This chapter describes the important roles of nonclassical C–H hydrogen bonds in asymmetric catalysis. Recently, many asymmetric catalytic reactions have demonstrated that weak C–H hydrogen bond interactions play important roles in selectivity. This chapter introduces the historical background of C–H hydrogen bonds, describes computational analyses of C–H hydrogen bonds in asymmetric catalysis and presents notable examples of asymmetric catalytic reactions in which C–H hydrogen bonds play important roles in selectivity.
{"title":"CHAPTER 2. Importance of C–H Hydrogen Bonding in Asymmetric Catalysis","authors":"S. Arimitsu, M. Higashi","doi":"10.1039/9781788016490-00026","DOIUrl":"https://doi.org/10.1039/9781788016490-00026","url":null,"abstract":"This chapter describes the important roles of nonclassical C–H hydrogen bonds in asymmetric catalysis. Recently, many asymmetric catalytic reactions have demonstrated that weak C–H hydrogen bond interactions play important roles in selectivity. This chapter introduces the historical background of C–H hydrogen bonds, describes computational analyses of C–H hydrogen bonds in asymmetric catalysis and presents notable examples of asymmetric catalytic reactions in which C–H hydrogen bonds play important roles in selectivity.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89526270","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}
Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00188
A. Bose, Saikat Maiti, P. Mal
Chemical reactions controlled by the systems involved are essential to elucidate the complex functions of living systems and create new functional molecules. This chapter proposes the utilization of simultaneous cooperative multiple weak interactions or soft forces in the synthesis of C–N bonds. In general, metal-mediated synthetic methods for the syntheses of C–N bonds are associated with drawbacks, e.g. (a) requirements for prefunctionalized starting materials, for example aryl halides, prior to the amination (making overall transformation multi-step in nature), and (b) production of stoichiometric amounts of metal halides as waste after the amination. In contrast, by performing C–N coupling reactions via direct C–H activation or functionalization (without using any prefunctionalized systems), many amination reactions can be successfully achieved. This chapter mainly covers selective C–N bond formation reactions under mild conditions with the intention that the reactivity of those systems could be controlled through soft forces or cooperative noncovalent interactions.
{"title":"CHAPTER 9. Soft Forces in Organic Synthesis by C–N Coupling Reactions","authors":"A. Bose, Saikat Maiti, P. Mal","doi":"10.1039/9781788016490-00188","DOIUrl":"https://doi.org/10.1039/9781788016490-00188","url":null,"abstract":"Chemical reactions controlled by the systems involved are essential to elucidate the complex functions of living systems and create new functional molecules. This chapter proposes the utilization of simultaneous cooperative multiple weak interactions or soft forces in the synthesis of C–N bonds. In general, metal-mediated synthetic methods for the syntheses of C–N bonds are associated with drawbacks, e.g. (a) requirements for prefunctionalized starting materials, for example aryl halides, prior to the amination (making overall transformation multi-step in nature), and (b) production of stoichiometric amounts of metal halides as waste after the amination. In contrast, by performing C–N coupling reactions via direct C–H activation or functionalization (without using any prefunctionalized systems), many amination reactions can be successfully achieved. This chapter mainly covers selective C–N bond formation reactions under mild conditions with the intention that the reactivity of those systems could be controlled through soft forces or cooperative noncovalent interactions.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84829293","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}
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