Pub Date : 2017-09-15DOI: 10.1002/9780470682531.PAT0920
A. Balaban
Electron paramagnetic resonance spectroscopy is at present the preferred method for studying free radicals. Push–pull aminyls show exceptional stability, which is explained satisfactorily by Linnett's double-quartet theory in terms of electronic spin. Stable hydrazyls such as 2,2-diphenyl-1-picrylhydrazyl and 2,2-diphenyl-1-cyanohydrazyl can actually be viewed as push–pull aminyls. A consequence of Linnett's theory is the increased bond order for the NN bond in hydrazyls, which is confirmed experimentally by X-ray crystallography and the high intramolecular rotation barrier. For aminyls and hydrazyls whose nitrogen center is not part of a ring, this survey lists the variety of electron donors and electron acceptors known so far. Keywords: aminyl and hydrazyl stable free radicals; nitrogen-centered persistent free radicals; push–pull stabilization; capto-dative stabilization; merostabilization; electron paramagnetic resonance spectra
{"title":"Stable Hydrazyls and Push–Pull (Capto-Dative) Aminyl Free Radicals","authors":"A. Balaban","doi":"10.1002/9780470682531.PAT0920","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0920","url":null,"abstract":"Electron paramagnetic resonance spectroscopy is at present the preferred method for studying free radicals. Push–pull aminyls show exceptional stability, which is explained satisfactorily by Linnett's double-quartet theory in terms of electronic spin. Stable hydrazyls such as 2,2-diphenyl-1-picrylhydrazyl and 2,2-diphenyl-1-cyanohydrazyl can actually be viewed as push–pull aminyls. A consequence of Linnett's theory is the increased bond order for the NN bond in hydrazyls, which is confirmed experimentally by X-ray crystallography and the high intramolecular rotation barrier. For aminyls and hydrazyls whose nitrogen center is not part of a ring, this survey lists the variety of electron donors and electron acceptors known so far. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aminyl and hydrazyl stable free radicals; \u0000nitrogen-centered persistent free radicals; \u0000push–pull stabilization; \u0000capto-dative stabilization; \u0000merostabilization; \u0000electron paramagnetic resonance spectra","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"87 1","pages":"1-9"},"PeriodicalIF":0.0,"publicationDate":"2017-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85628117","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 : 2017-09-15DOI: 10.1002/9780470682531.PAT0848
E. L. Bastos, C. O. Machado
This chapter is an update of a recent review on the acid–base chemistry and solvation properties of metal phenolates. After a brief introduction on the physicochemical properties of metal phenolates, the interaction between phenolate ligands and metal Lewis acids is discussed. Examples of solvent effects on the acid–base properties, structure, and chemical reactivity are presented. Furthermore, the interaction of multidentate phenolic ligands and metal cations is highlighted because of their relevance in transition-metal coordination chemistry, catalyst development, metalloenzyme mimicry, cytotoxicity, and magnetic properties. Keywords: metal phenolates; solvent effects; acid–base equilibrium
{"title":"Recent Advances in Acid–Base and Solvation Properties of Metal Phenolates","authors":"E. L. Bastos, C. O. Machado","doi":"10.1002/9780470682531.PAT0848","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0848","url":null,"abstract":"This chapter is an update of a recent review on the acid–base chemistry and solvation properties of metal phenolates. After a brief introduction on the physicochemical properties of metal phenolates, the interaction between phenolate ligands and metal Lewis acids is discussed. Examples of solvent effects on the acid–base properties, structure, and chemical reactivity are presented. Furthermore, the interaction of multidentate phenolic ligands and metal cations is highlighted because of their relevance in transition-metal coordination chemistry, catalyst development, metalloenzyme mimicry, cytotoxicity, and magnetic properties. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metal phenolates; \u0000solvent effects; \u0000acid–base equilibrium","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"25 1","pages":"1-60"},"PeriodicalIF":0.0,"publicationDate":"2017-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89096689","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 : 2017-09-15DOI: 10.1002/9780470682531.PAT0937
E. L. Bastos
This chapter presents the main aspects of acid–base reactions of transition-metal enolates and an overview of solvent effects on the chemical reactivity of metal enolates. Keywords: enolate ion; transition-metal enolates; metal Lewis acids; dissociation constants; solvent effects; acid–base equilibrium
{"title":"Acid–Base and Solvation Properties of Metal Enolates Part 2: Transition-Metal Enolates and Medium Effects","authors":"E. L. Bastos","doi":"10.1002/9780470682531.PAT0937","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0937","url":null,"abstract":"This chapter presents the main aspects of acid–base reactions of transition-metal enolates and an overview of solvent effects on the chemical reactivity of metal enolates. \u0000 \u0000 \u0000Keywords: \u0000 \u0000enolate ion; \u0000transition-metal enolates; \u0000metal Lewis acids; \u0000dissociation constants; \u0000solvent effects; \u0000acid–base equilibrium","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"16 1","pages":"1-61"},"PeriodicalIF":0.0,"publicationDate":"2017-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76804984","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 : 2017-08-15DOI: 10.1002/9780470682531.PAT0932
Maja Ponikvar‑Svet, J. Liebman
The chapter deals with the contemporary use of azophenolates and related species in the determination of metal ions. Structural variety of azophenolates is discussed. Many of the metals have more than one oxidation state (valence). Only one oxidation state was chosen for each metal (atomic number between 3 and 56) as an example. Principles of the procedures in which azophenolate reagents are used for analytical purposes are described, and important details on individual analytical procedures are listed. Keywords: contemporary; metal cations; azophenolates; determination; methods
{"title":"Contemporary Use of Azophenolates and Related Species in the Determination of Metal Cations","authors":"Maja Ponikvar‑Svet, J. Liebman","doi":"10.1002/9780470682531.PAT0932","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0932","url":null,"abstract":"The chapter deals with the contemporary use of azophenolates and related species in the determination of metal ions. Structural variety of azophenolates is discussed. Many of the metals have more than one oxidation state (valence). Only one oxidation state was chosen for each metal (atomic number between 3 and 56) as an example. Principles of the procedures in which azophenolate reagents are used for analytical purposes are described, and important details on individual analytical procedures are listed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000contemporary; \u0000metal cations; \u0000azophenolates; \u0000determination; \u0000methods","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2017-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81641373","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 : 2017-08-15DOI: 10.1002/9780470682531.PAT0912
D. N. Zeiger, J. Liebman, Maja Ponikvar‑Svet
In this chapter, we will discuss diverse aspects of the energetics of metal β-diketonates and their derivatives. By “energetics” we mean thermochemical and related studies, and so we include enthalpies of reaction and of formation as well as equilibrium measurements and stability constants. We will also discuss the gain or loss of an electron, and therefore consider ionization potentials, electron affinities, and electrochemical potentials. By metal β-diketonates and derivatives we mean, most generally, species with a substructure of the type [M(dik)n], where dik (β-diketonato) is an organic monovalent anion of structure (RC(X)C(R1)C(O)R2)− and M is an arbitrary metal. For completeness and additional insights, in this chapter we will also consider M to be virtually all elements (nonmetal, metalloid, or metal), and eventually we will include hydrogen. Keywords: acetylacetonates; diketonates; enthalpy; metal chelates; metal complexes; metalloid; nonmetal; thermochemistry
{"title":"Aspects of the Energetics of Metal β-Diketonates and their Derivatives","authors":"D. N. Zeiger, J. Liebman, Maja Ponikvar‑Svet","doi":"10.1002/9780470682531.PAT0912","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0912","url":null,"abstract":"In this chapter, we will discuss diverse aspects of the energetics of metal β-diketonates and their derivatives. By “energetics” we mean thermochemical and related studies, and so we include enthalpies of reaction and of formation as well as equilibrium measurements and stability constants. We will also discuss the gain or loss of an electron, and therefore consider ionization potentials, electron affinities, and electrochemical potentials. By metal β-diketonates and derivatives we mean, most generally, species with a substructure of the type [M(dik)n], where dik (β-diketonato) is an organic monovalent anion of structure (RC(X)C(R1)C(O)R2)− and M is an arbitrary metal. For completeness and additional insights, in this chapter we will also consider M to be virtually all elements (nonmetal, metalloid, or metal), and eventually we will include hydrogen. \u0000 \u0000 \u0000Keywords: \u0000 \u0000acetylacetonates; \u0000diketonates; \u0000enthalpy; \u0000metal chelates; \u0000metal complexes; \u0000metalloid; \u0000nonmetal; \u0000thermochemistry","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2017-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73165933","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 : 2017-01-26DOI: 10.1002/9780470682531.PAT0837
I. Shterenberg, Michael Salama, Y. Gofer, D. Aurbach
In this chapter, selected and the most important aspects of the electrochemistry of organoaluminum compounds are described. It is focused on two main implementations: electrochemical aluminum plating and rechargeable Mg batteries. Electrochemical aspects of organoaluminum-based electroplating baths are discussed in detail and the effects of the solutions formulation on the electrochemical properties are explained. The role of organoaluminum compounds, acting as Lewis acids, in the formulation of the electrolyte solutions for rechargeable Mg batteries, and their effect on the performance of electrolyte solutions is described. Keywords: aluminum; organoaluminum compounds; electrodeposition; ionic liquids; magnesium batteries; non-aqueous electrochemistry
{"title":"Electrochemistry of Organoaluminum Compounds","authors":"I. Shterenberg, Michael Salama, Y. Gofer, D. Aurbach","doi":"10.1002/9780470682531.PAT0837","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0837","url":null,"abstract":"In this chapter, selected and the most important aspects of the electrochemistry of organoaluminum compounds are described. It is focused on two main implementations: electrochemical aluminum plating and rechargeable Mg batteries. Electrochemical aspects of organoaluminum-based electroplating baths are discussed in detail and the effects of the solutions formulation on the electrochemical properties are explained. The role of organoaluminum compounds, acting as Lewis acids, in the formulation of the electrolyte solutions for rechargeable Mg batteries, and their effect on the performance of electrolyte solutions is described. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aluminum; \u0000organoaluminum compounds; \u0000electrodeposition; \u0000ionic liquids; \u0000magnesium batteries; \u0000non-aqueous electrochemistry","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"1 1","pages":"1-18"},"PeriodicalIF":0.0,"publicationDate":"2017-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90322189","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 : 2017-01-11DOI: 10.1002/9780470682531.PAT0915
P. Cragg, P. M. Marcos
Thiacalixarenes are members of the calixarene family in which sulfur has replaced one or more of the methylene bridges between the phenolic moieties of the macrocycles. Oxidation of the thiacalixarenes leads to sulfinyl and sulfonyl homologs. The incorporation of sulfur affects the metal-binding affinities of these calixarenes over their all-carbon analogs through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. Other binding motifs are possible for the oxidized thiacalixarenes leading to a vast array of complexes with metal cations. This chapter covers the literature concerning thiacalixarenes containing free OH groups at the lower rim since they were first reported. Their coordination chemistry toward alkali, alkaline earth, transition, heavy, lanthanide, and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, transition-metal extraction, and cation transport. Keywords: thiacalixarenes; metal phenolates; coordination chemistry; metal complexes; alkali and alkaline earth metals; transition and heavy metals; lanthanide and actinide metals
{"title":"Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes","authors":"P. Cragg, P. M. Marcos","doi":"10.1002/9780470682531.PAT0915","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0915","url":null,"abstract":"Thiacalixarenes are members of the calixarene family in which sulfur has replaced one or more of the methylene bridges between the phenolic moieties of the macrocycles. Oxidation of the thiacalixarenes leads to sulfinyl and sulfonyl homologs. The incorporation of sulfur affects the metal-binding affinities of these calixarenes over their all-carbon analogs through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. Other binding motifs are possible for the oxidized thiacalixarenes leading to a vast array of complexes with metal cations. This chapter covers the literature concerning thiacalixarenes containing free OH groups at the lower rim since they were first reported. Their coordination chemistry toward alkali, alkaline earth, transition, heavy, lanthanide, and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, transition-metal extraction, and cation transport. \u0000 \u0000 \u0000Keywords: \u0000 \u0000thiacalixarenes; \u0000metal phenolates; \u0000coordination chemistry; \u0000metal complexes; \u0000alkali and alkaline earth metals; \u0000transition and heavy metals; \u0000lanthanide and actinide metals","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"101 1","pages":"1-32"},"PeriodicalIF":0.0,"publicationDate":"2017-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84016166","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 : 2016-12-19DOI: 10.1002/9780470682531.PAT0838
R. Wehmschulte
During the past 25 plus years, room-temperature stable aluminum(I) and (II) compounds have become available through standard organometallic techniques, and their reactivity has been explored in much detail. The chemistry of aluminum(I) compounds may be viewed as that of a very reactive carbene (singlet and triplet, depending on the substrate). Typical reactions involve insertions into various EE or EX bonds and adduct formation with Lewis acids. Aluminum(II) compounds are generally dialumenes (R2AlAlR2) featuring an AlAl single bond. Their chemistry is similar to that of alanes (R3Al) with respect to substitutions and Lewis acid base chemistry but with a strong redox component. In many cases, substrates insert into the AlAl bond in a formally oxidative manner. Keywords: aluminum; low oxidation state; dialumane; dialumene; reduction; insertion; Lewis acid; Lewis base; carbene; insertion
{"title":"The Chemistry of Low-Valent Organoaluminum Species","authors":"R. Wehmschulte","doi":"10.1002/9780470682531.PAT0838","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0838","url":null,"abstract":"During the past 25 plus years, room-temperature stable aluminum(I) and (II) compounds have become available through standard organometallic techniques, and their reactivity has been explored in much detail. The chemistry of aluminum(I) compounds may be viewed as that of a very reactive carbene (singlet and triplet, depending on the substrate). Typical reactions involve insertions into various EE or EX bonds and adduct formation with Lewis acids. Aluminum(II) compounds are generally dialumenes (R2AlAlR2) featuring an AlAl single bond. Their chemistry is similar to that of alanes (R3Al) with respect to substitutions and Lewis acid base chemistry but with a strong redox component. In many cases, substrates insert into the AlAl bond in a formally oxidative manner. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aluminum; \u0000low oxidation state; \u0000dialumane; \u0000dialumene; \u0000reduction; \u0000insertion; \u0000Lewis acid; \u0000Lewis base; \u0000carbene; \u0000insertion","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"13 1","pages":"1-30"},"PeriodicalIF":0.0,"publicationDate":"2016-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84965203","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 : 2016-10-17DOI: 10.1002/9780470682531.PAT0839
M. Layh, W. Uhl, G. Bouhadir, D. Bourissou
This chapter is dedicated to bifunctional derivatives associating Al with P- or N-containing Lewis bases. The synthesis and structure of these Lewis pairs/ambiphilic derivatives are described (presence or not of P/N Al interactions). Both unimolecular and bimolecular compounds are considered. Their reactivity towards small molecules (CO2, alkene, alkynes, isocyanides, amine-boranes, BX3, hydrides, and so on) including catalytic transformations are then presented. The synthesis and reactivity of transition metal complexes deriving from Al/P ambiphilic ligands are also presented. Whenever possible, the Al-compounds are compared to their lighter B congeners. Keywords: σ-acceptor; activation; ambiphilic; aluminum; bifunctional; catalysis; frustrated Lewis pairs; M Al interactions; Lewis acids; ligands; phosphines; small molecules
{"title":"Organoaluminum Compounds and Lewis Pairs","authors":"M. Layh, W. Uhl, G. Bouhadir, D. Bourissou","doi":"10.1002/9780470682531.PAT0839","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0839","url":null,"abstract":"This chapter is dedicated to bifunctional derivatives associating Al with P- or N-containing Lewis bases. The synthesis and structure of these Lewis pairs/ambiphilic derivatives are described (presence or not of P/N Al interactions). Both unimolecular and bimolecular compounds are considered. Their reactivity towards small molecules (CO2, alkene, alkynes, isocyanides, amine-boranes, BX3, hydrides, and so on) including catalytic transformations are then presented. The synthesis and reactivity of transition metal complexes deriving from Al/P ambiphilic ligands are also presented. Whenever possible, the Al-compounds are compared to their lighter B congeners. \u0000 \u0000 \u0000Keywords: \u0000 \u0000σ-acceptor; \u0000activation; \u0000ambiphilic; \u0000aluminum; \u0000bifunctional; \u0000catalysis; \u0000frustrated Lewis pairs; \u0000M Al interactions; \u0000Lewis acids; \u0000ligands; \u0000phosphines; \u0000small molecules","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"10 1","pages":"1-46"},"PeriodicalIF":0.0,"publicationDate":"2016-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84107121","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 : 2016-09-28DOI: 10.1002/9780470682531.PAT0847
P. M. Marcos, P. Cragg
Heteracalixarenes are members of the calixarene family in which heteroatoms such as oxygen, nitrogen, sulfur, selenium, or silicon are inserted between the methylene bridges or replace them entirely. The incorporation of heteroatoms affects the metal binding affinities of these calixarenes over their all-carbon analogues, through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. This chapter covers the literature concerning phenolic homooxa- and homoazacalixarene-metal complexes mainly for the last two decades (1994–2014). The syntheses of homooxa- and homoazacalixarenes containing free OH groups at the lower rim are described and their coordination chemistry towards alkali, alkaline earth, transition, heavy, lanthanide and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, and metal cation extraction and transport. Keywords: alkali and alkaline earth metals; coordination chemistry; homoazacalixarenes; homooxacalixarenes; lanthanide and actinide metals; metal phenolates; metal complexes; transition and heavy metals
{"title":"Coordination Chemistry and Applications of Phenolic Homooxa‐ and Homoazacalixarene–Metal Complexes","authors":"P. M. Marcos, P. Cragg","doi":"10.1002/9780470682531.PAT0847","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0847","url":null,"abstract":"Heteracalixarenes are members of the calixarene family in which heteroatoms such as oxygen, nitrogen, sulfur, selenium, or silicon are inserted between the methylene bridges or replace them entirely. The incorporation of heteroatoms affects the metal binding affinities of these calixarenes over their all-carbon analogues, through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. This chapter covers the literature concerning phenolic homooxa- and homoazacalixarene-metal complexes mainly for the last two decades (1994–2014). The syntheses of homooxa- and homoazacalixarenes containing free OH groups at the lower rim are described and their coordination chemistry towards alkali, alkaline earth, transition, heavy, lanthanide and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, and metal cation extraction and transport. \u0000 \u0000 \u0000Keywords: \u0000 \u0000alkali and alkaline earth metals; \u0000coordination chemistry; \u0000homoazacalixarenes; \u0000homooxacalixarenes; \u0000lanthanide and actinide metals; \u0000metal phenolates; \u0000metal complexes; \u0000transition and heavy metals","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"12 1","pages":"195-235"},"PeriodicalIF":0.0,"publicationDate":"2016-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75258891","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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