Pub Date : 2019-03-04DOI: 10.1039/9781788016490-00527
Madhulika Gupta, T. Khan, Manish Agarwal, M. Haider
This chapter emphasizes the need for a fundamental understanding of the noncovalent interactions of amino acids with transition metal catalyst surfaces in aqueous systems. This understanding is essential for the growing development of the synthesis of bio-based fuels and chemicals using integrated fermentation and catalytic processing, wherein biogenic impurities (amino acids and protein residues) are observed to deactivate heterogeneous metal catalysts.
{"title":"CHAPTER 24. Noncovalent Interactions of Biogenic Impurities with Transition Metal Catalyst Surfaces","authors":"Madhulika Gupta, T. Khan, Manish Agarwal, M. Haider","doi":"10.1039/9781788016490-00527","DOIUrl":"https://doi.org/10.1039/9781788016490-00527","url":null,"abstract":"This chapter emphasizes the need for a fundamental understanding of the noncovalent interactions of amino acids with transition metal catalyst surfaces in aqueous systems. This understanding is essential for the growing development of the synthesis of bio-based fuels and chemicals using integrated fermentation and catalytic processing, wherein biogenic impurities (amino acids and protein residues) are observed to deactivate heterogeneous metal catalysts.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"145 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77051293","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: 10.1039/9781788016490-00153
A. Caminade
Dendrimers are nanometric macromolecules constituted of repetitive branched units, arranged radially around a central core. They are synthesized step-by-step, generally using a divergent process from this core. Dendrimers have many properties and, among them, catalysis is a major field. Two main area are studied, on the one hand the search for a positive “dendrimer effect,” i.e. an increase in catalytic efficiency when the size of the dendrimer increases, and on the other the encapsulation of catalytically active nanoparticles inside dendrimers. In both cases, noncovalent interactions are involved. This chapter discusses the important role played by noncovalent interactions in the properties of dendrimers in catalysis. The first part concerns the dendrimer effect, then a short section considers noncovalently formed catalytic dendrimers and the final part concerns dendrimers encapsulating catalytic nanoparticles.
{"title":"CHAPTER 7. The Role of Noncovalent Interactions in the Efficiency of Dendrimers in Catalysis","authors":"A. Caminade","doi":"10.1039/9781788016490-00153","DOIUrl":"https://doi.org/10.1039/9781788016490-00153","url":null,"abstract":"Dendrimers are nanometric macromolecules constituted of repetitive branched units, arranged radially around a central core. They are synthesized step-by-step, generally using a divergent process from this core. Dendrimers have many properties and, among them, catalysis is a major field. Two main area are studied, on the one hand the search for a positive “dendrimer effect,” i.e. an increase in catalytic efficiency when the size of the dendrimer increases, and on the other the encapsulation of catalytically active nanoparticles inside dendrimers. In both cases, noncovalent interactions are involved. This chapter discusses the important role played by noncovalent interactions in the properties of dendrimers in catalysis. The first part concerns the dendrimer effect, then a short section considers noncovalently formed catalytic dendrimers and the final part concerns dendrimers encapsulating catalytic nanoparticles.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"99 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78371021","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: 10.1039/9781788016490-00579
M. Hamdaoui, J. Djukic
This chapter covers the most recent advances in investigations of the most critical intermediates in transition metal-promoted processes with a main emphasis on metal-to-H–E bonding (mainly E = C, Si) interactions. After several decades of descriptive research on the interactions of C–H and Si–H bonds with coordinatively unsaturated metal centres, it is only recently that interest has risen in the role played by noncovalent interactions. It appears that recent advances in the understanding of so-called agostic interactions with metal centres demonstrate some control of the London force that the Dewar–Chatt–Duncanson model cannot sense. It is suggested that similar efforts should be generalized to other metal-to-H–E bonding interactions.
{"title":"CHAPTER 27. Noncovalent Interactions in Key Metal-centred Catalytic Intermediates: Structure–Electronic Relationship","authors":"M. Hamdaoui, J. Djukic","doi":"10.1039/9781788016490-00579","DOIUrl":"https://doi.org/10.1039/9781788016490-00579","url":null,"abstract":"This chapter covers the most recent advances in investigations of the most critical intermediates in transition metal-promoted processes with a main emphasis on metal-to-H–E bonding (mainly E = C, Si) interactions. After several decades of descriptive research on the interactions of C–H and Si–H bonds with coordinatively unsaturated metal centres, it is only recently that interest has risen in the role played by noncovalent interactions. It appears that recent advances in the understanding of so-called agostic interactions with metal centres demonstrate some control of the London force that the Dewar–Chatt–Duncanson model cannot sense. It is suggested that similar efforts should be generalized to other metal-to-H–E bonding interactions.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"38 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89542509","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: 10.1039/9781788016490-00302
S. Kurek, Piotr P Romańczyk
This chapter demonstrates how common are noncovalent interactions assisting catalytic reductive dehalogenation, including enzymatic reactions in reductive dehalogenases. Examples are given of halogen bonding, specific to the reactants in this process, facilitating it, but also hydrogen bonding, which may make the carbon–halogen bond more prone to cleavage or even provide a path for the electron transfer. Various types of noncovalent interactions locate the enzyme substrate in a position ideal for dehalogenation to proceed. Such systems are described, and also model systems, in which proximity effects have been shown to operate. The importance of quantum-chemical calculations in the discovery of noncovalent effects and revealing their significance for the efficiency and selectivity of reductive dehalogenation is also stressed.
{"title":"CHAPTER 14. Noncovalent Interaction-assisted Redox Catalysis in Reductive Dehalogenation","authors":"S. Kurek, Piotr P Romańczyk","doi":"10.1039/9781788016490-00302","DOIUrl":"https://doi.org/10.1039/9781788016490-00302","url":null,"abstract":"This chapter demonstrates how common are noncovalent interactions assisting catalytic reductive dehalogenation, including enzymatic reactions in reductive dehalogenases. Examples are given of halogen bonding, specific to the reactants in this process, facilitating it, but also hydrogen bonding, which may make the carbon–halogen bond more prone to cleavage or even provide a path for the electron transfer. Various types of noncovalent interactions locate the enzyme substrate in a position ideal for dehalogenation to proceed. Such systems are described, and also model systems, in which proximity effects have been shown to operate. The importance of quantum-chemical calculations in the discovery of noncovalent effects and revealing their significance for the efficiency and selectivity of reductive dehalogenation is also stressed.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"14 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86144540","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: 10.1039/9781788016490-00324
K. J. Johnson, Keaton V. Prather, James D. Blakemore
Molecular metal complexes and other redox-active species can be usefully incorporated into functional devices by attachment or immobilization on electrodes as solid supports. Stable adhesion of the complexes to electrode surfaces can be driven by covalent or noncovalent interactions. This chapter surveys the use of polyaromatic hydrocarbon moieties, chiefly the pyrene group, to immobilize redox-active species noncovalently onto electrode surfaces. Synthetic incorporation of pyrenyl groups onto core catalyst structures is shown to be attractive for its simplicity and it is generally effective in enabling studies of surface-immobilized redox chemistry and catalysis. Efforts reported in the literature to improve stability, electron-transfer kinetics and long-term catalyst viability are specifically highlighted. A summary and outlook section provides a brief discussion of key challenges to the field and opportunities for future developments in this rapidly evolving area.
{"title":"CHAPTER 15. Noncovalent Immobilization of Catalysts on Electrode Surfaces","authors":"K. J. Johnson, Keaton V. Prather, James D. Blakemore","doi":"10.1039/9781788016490-00324","DOIUrl":"https://doi.org/10.1039/9781788016490-00324","url":null,"abstract":"Molecular metal complexes and other redox-active species can be usefully incorporated into functional devices by attachment or immobilization on electrodes as solid supports. Stable adhesion of the complexes to electrode surfaces can be driven by covalent or noncovalent interactions. This chapter surveys the use of polyaromatic hydrocarbon moieties, chiefly the pyrene group, to immobilize redox-active species noncovalently onto electrode surfaces. Synthetic incorporation of pyrenyl groups onto core catalyst structures is shown to be attractive for its simplicity and it is generally effective in enabling studies of surface-immobilized redox chemistry and catalysis. Efforts reported in the literature to improve stability, electron-transfer kinetics and long-term catalyst viability are specifically highlighted. A summary and outlook section provides a brief discussion of key challenges to the field and opportunities for future developments in this rapidly evolving area.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75461685","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: 10.1039/9781788016490-00253
A. Phillips
Noncovalent interactions play an important role in enzyme catalysis, helping to stabilize transition states. Favourable interactions, including hydrogen bonding, π-stacking, CH⋯π and lone pair⋯π interactions, amongst others, may also be responsible for the regioselectivity and high degrees of stereoselectivity that can be achieved with some small-molecule catalysts. Noncovalent interactions often compete with steric effects and identifying and understanding them is not always straightforward. Nevertheless, this can provide a basis for the rational design of new catalysts, to be applied in the synthesis of single enantiomers needed for various applications ranging from pharmaceuticals to advanced materials. This chapter provides an overview of recent findings in the area of chiral phosphoric acid-catalysed reactions. It considers the types of reactions and the modes of activation possible, the models used to predict stereoselectivity and the types of interactions involved. A few case studies selected from the recent literature illustrate the state-of-the-art in this important branch of catalysis.
{"title":"CHAPTER 12. Noncovalent Interactions in Asymmetric Reactions Catalysed by Chiral Phosphoric Acids","authors":"A. Phillips","doi":"10.1039/9781788016490-00253","DOIUrl":"https://doi.org/10.1039/9781788016490-00253","url":null,"abstract":"Noncovalent interactions play an important role in enzyme catalysis, helping to stabilize transition states. Favourable interactions, including hydrogen bonding, π-stacking, CH⋯π and lone pair⋯π interactions, amongst others, may also be responsible for the regioselectivity and high degrees of stereoselectivity that can be achieved with some small-molecule catalysts. Noncovalent interactions often compete with steric effects and identifying and understanding them is not always straightforward. Nevertheless, this can provide a basis for the rational design of new catalysts, to be applied in the synthesis of single enantiomers needed for various applications ranging from pharmaceuticals to advanced materials. This chapter provides an overview of recent findings in the area of chiral phosphoric acid-catalysed reactions. It considers the types of reactions and the modes of activation possible, the models used to predict stereoselectivity and the types of interactions involved. A few case studies selected from the recent literature illustrate the state-of-the-art in this important branch of catalysis.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"52 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88443827","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: 10.1039/9781788016490-00393
M. C. D’Alterio, C. Rosa, G. Talarico
Two case histories are reported where noncovalent interactions play an important role in olefin polymerization catalyzed by transition metals. In the first example, by using DFT calculations, the influence of α-agostic interactions on the stereoselectivity of propene insertion reactions and their contribution to developing new models for the isotactic stereocontrol achieved with nonmetallocene catalysts are considered. In the second example, experimental and theoretical results aimed at explaining the role of noncovalent interactions (such as F⋯H or F⋯M, where M = metal center) in living olefin polymerization promoted by Group 4 nonmetallocene systems and also the chain-branching formation of polyethylene obtained with late transition metals are summarized.
{"title":"CHAPTER 18. Noncovalent Interactions in Olefin Polymerization Catalysis Promoted by Transition Metals","authors":"M. C. D’Alterio, C. Rosa, G. Talarico","doi":"10.1039/9781788016490-00393","DOIUrl":"https://doi.org/10.1039/9781788016490-00393","url":null,"abstract":"Two case histories are reported where noncovalent interactions play an important role in olefin polymerization catalyzed by transition metals. In the first example, by using DFT calculations, the influence of α-agostic interactions on the stereoselectivity of propene insertion reactions and their contribution to developing new models for the isotactic stereocontrol achieved with nonmetallocene catalysts are considered. In the second example, experimental and theoretical results aimed at explaining the role of noncovalent interactions (such as F⋯H or F⋯M, where M = metal center) in living olefin polymerization promoted by Group 4 nonmetallocene systems and also the chain-branching formation of polyethylene obtained with late transition metals are summarized.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"109 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79194795","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: 10.1039/9781788016490-00122
R. Gomila, A. Frontera
The anion–π interaction is nowadays considered as a consolidated member of the supramolecular weak interactions family. In its naissance, it was mostly used in host–guest chemistry for the molecular recognition of anions. Nowadays its application to the construction of functional systems is attracting considerable attention. In this context, the anion–π interaction has become a prominent player in noncovalent catalysis since anionic intermediates can be conveniently stabilized on π-acidic surfaces. Remarkably, examples embrace enolate, enamine and iminium chemistry, domino processes and Diels–Alder reactions. Moreover, it is worth highlighting the recent appearance in the literature of the first example of asymmetric anion–π catalysis of cascade reactions that afford nonadjacent stereocentres. The anion–π catalysts are usually constructed using naphthalenediimide and/or fullerene building blocks, which present extended π-acidic surfaces along with high polarizabilities and are thus well suited for establishing anion–π interactions. In this chapter, we review the general concept of anion–π catalysis. It is based on the stabilization of anionic transition states and intermediates by anion–π interactions on π-acidic aromatic surfaces. Since 2013, anion–π catalysis has been explored with several reactions. In addition, anion–π enzymes and electric field-assisted anion–π catalysis are also described.
{"title":"CHAPTER 5. Anion–π Catalysis","authors":"R. Gomila, A. Frontera","doi":"10.1039/9781788016490-00122","DOIUrl":"https://doi.org/10.1039/9781788016490-00122","url":null,"abstract":"The anion–π interaction is nowadays considered as a consolidated member of the supramolecular weak interactions family. In its naissance, it was mostly used in host–guest chemistry for the molecular recognition of anions. Nowadays its application to the construction of functional systems is attracting considerable attention. In this context, the anion–π interaction has become a prominent player in noncovalent catalysis since anionic intermediates can be conveniently stabilized on π-acidic surfaces. Remarkably, examples embrace enolate, enamine and iminium chemistry, domino processes and Diels–Alder reactions. Moreover, it is worth highlighting the recent appearance in the literature of the first example of asymmetric anion–π catalysis of cascade reactions that afford nonadjacent stereocentres. The anion–π catalysts are usually constructed using naphthalenediimide and/or fullerene building blocks, which present extended π-acidic surfaces along with high polarizabilities and are thus well suited for establishing anion–π interactions. In this chapter, we review the general concept of anion–π catalysis. It is based on the stabilization of anionic transition states and intermediates by anion–π interactions on π-acidic aromatic surfaces. Since 2013, anion–π catalysis has been explored with several reactions. In addition, anion–π enzymes and electric field-assisted anion–π catalysis are also described.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"17 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72679027","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: 10.1039/9781788016490-00094
Y. Sarazin, J. Carpentier
The design and implementation of a selection of homogeneous alkaline earth (Ae) catalysts and precatalysts for hydroamination and hydrophosphination of olefins and for ring-opening polymerization of cyclic esters are surveyed. Emphasis is placed on the three large elements calcium, strontium and barium. The role of Ae⋯H–Si and Ae⋯F–C noncovalent interactions in the stabilization of (pre)catalysts is highlighted.
{"title":"CHAPTER 4. Secondary (Agostic Si–H/Electrostatic C–F) Interactions in Alkaline Earth-based Catalysts","authors":"Y. Sarazin, J. Carpentier","doi":"10.1039/9781788016490-00094","DOIUrl":"https://doi.org/10.1039/9781788016490-00094","url":null,"abstract":"The design and implementation of a selection of homogeneous alkaline earth (Ae) catalysts and precatalysts for hydroamination and hydrophosphination of olefins and for ring-opening polymerization of cyclic esters are surveyed. Emphasis is placed on the three large elements calcium, strontium and barium. The role of Ae⋯H–Si and Ae⋯F–C noncovalent interactions in the stabilization of (pre)catalysts is highlighted.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"61 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78352378","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: 10.1039/9781788016490-00209
N. Momiyama
Chiral Bronsted acid catalysis is one of the most important tool in asymmetric synthesis. To achieve good reaction efficiency and selectivity, noncovalent interactions such as hydrogen bonding have been a key factor in the design of chiral Bronsted acid catalysts. Recent contributions in this area are summarized in this chapter.
{"title":"CHAPTER 10. Noncovalent Interactions in the Design of Chiral Brønsted Acid Catalysts","authors":"N. Momiyama","doi":"10.1039/9781788016490-00209","DOIUrl":"https://doi.org/10.1039/9781788016490-00209","url":null,"abstract":"Chiral Bronsted acid catalysis is one of the most important tool in asymmetric synthesis. To achieve good reaction efficiency and selectivity, noncovalent interactions such as hydrogen bonding have been a key factor in the design of chiral Bronsted acid catalysts. Recent contributions in this area are summarized in this chapter.","PeriodicalId":10054,"journal":{"name":"Catalysis Series","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73959679","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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