Pub Date : 2016-09-28DOI: 10.1002/9780470682531.PAT0859
M. Arisawa, M. Yamaguchi
Metal enolates are versatile nucleophilic reagents in organic synthesis, and are applicable to reactions with various electrophiles. The reactivity of transition metal enolates differs from that of enolates derived from main-group elements, although such reaction is rare other than for palladium and copper enolates. The focus in this chapter is formation and reaction of rhodium enolates, the following features of which are notable: (i) rhodium can assume various oxidation states and coordination modes; (ii) O-bound rhodium enolates have a low RhO bond polarity, because the difference in electronegativity between rhodium and oxygen is considerably smaller than that between lithium and oxygen, and the compounds show less basisity but modest nucleophilicity; (iii) oxidative addition and reductive elimination can be employed to form, react, and regenerate rhodium enolates; (iv) modest reactivity allows the use of various methods to control the reactivity and includes tolerance for various cosubstrates and metal reagents; (v) regeneration of rhodium enolates allows catalysis; (vi) use of chiral ligands allows applications to asymmetric reactions. Therefore, rhodium enolates react with various reagents, such as aldehydes, water, perfluoroalkyl iodides, perfluorobenzenes, arylboranes, aryltitaniums, disulfides, α-organothioketones, and ketones. Rhodium enolates can become important synthetic intermediates possessing diverse of reactivities in organic synthesis. Keywords: rhodium enolates; catalysis; modest nucleophilicity; low basisity; carbonyl compounds; 1,4-addition; transmetallation; retro-aldol reaction; CS bond cleavage and formation; α-deprotonation
{"title":"Rhodium Enolate Complexes as Synthons and Catalysts in Organic Chemistry","authors":"M. Arisawa, M. Yamaguchi","doi":"10.1002/9780470682531.PAT0859","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0859","url":null,"abstract":"Metal enolates are versatile nucleophilic reagents in organic synthesis, and are applicable to reactions with various electrophiles. The reactivity of transition metal enolates differs from that of enolates derived from main-group elements, although such reaction is rare other than for palladium and copper enolates. The focus in this chapter is formation and reaction of rhodium enolates, the following features of which are notable: (i) rhodium can assume various oxidation states and coordination modes; (ii) O-bound rhodium enolates have a low RhO bond polarity, because the difference in electronegativity between rhodium and oxygen is considerably smaller than that between lithium and oxygen, and the compounds show less basisity but modest nucleophilicity; (iii) oxidative addition and reductive elimination can be employed to form, react, and regenerate rhodium enolates; (iv) modest reactivity allows the use of various methods to control the reactivity and includes tolerance for various cosubstrates and metal reagents; (v) regeneration of rhodium enolates allows catalysis; (vi) use of chiral ligands allows applications to asymmetric reactions. Therefore, rhodium enolates react with various reagents, such as aldehydes, water, perfluoroalkyl iodides, perfluorobenzenes, arylboranes, aryltitaniums, disulfides, α-organothioketones, and ketones. Rhodium enolates can become important synthetic intermediates possessing diverse of reactivities in organic synthesis. \u0000 \u0000 \u0000Keywords: \u0000 \u0000rhodium enolates; \u0000catalysis; \u0000modest nucleophilicity; \u0000low basisity; \u0000carbonyl compounds; \u00001,4-addition; \u0000transmetallation; \u0000retro-aldol reaction; \u0000CS bond cleavage and formation; \u0000α-deprotonation","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"55 1","pages":"1-42"},"PeriodicalIF":0.0,"publicationDate":"2016-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81099935","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 : 2016-09-19DOI: 10.1002/9780470682531.PAT0853
S. Dagorne, C. Romain
The present contribution provides a broad overview on the latest significant developments on metal phenolate complexes for use in polymerization catalysis of olefins, cyclic esters, and cyclic carbonates. Systems mediating the CO2/epoxide polymerization are also especially emphasized. Keywords: catalysis; carbon dioxide; diene; epoxide; lactide; metal; olefin; phenolate; polymerization
{"title":"Polymerization Catalysis by Metal Phenolates","authors":"S. Dagorne, C. Romain","doi":"10.1002/9780470682531.PAT0853","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0853","url":null,"abstract":"The present contribution provides a broad overview on the latest significant developments on metal phenolate complexes for use in polymerization catalysis of olefins, cyclic esters, and cyclic carbonates. Systems mediating the CO2/epoxide polymerization are also especially emphasized. \u0000 \u0000 \u0000Keywords: \u0000 \u0000catalysis; \u0000carbon dioxide; \u0000diene; \u0000epoxide; \u0000lactide; \u0000metal; \u0000olefin; \u0000phenolate; \u0000polymerization","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"53 1","pages":"1-44"},"PeriodicalIF":0.0,"publicationDate":"2016-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75743534","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 : 2016-06-21DOI: 10.1002/9780470682531.PAT0910
H. Lang, David Adner, C. Georgi
This chapter is an update of part of a review published by our group elsewhere in Patai's Series; in addition, in this volume, chapters present the recent advances in the deposition of metals and oxides of main-group metals and rare-earth elements, all derived from metal enolates. Metal oxides are essential as common inorganic crude materials, possessing a manifold portfolio of applications because of their singular physical and chemical properties. Metal oxides are formed by straight vaporization from metal oxide sources, by evaporation of metals in an oxidizing atmosphere, or via wet chemistry, for example, the sol-gel process. Their industrial use includes protective coatings, electrical insulator materials, gate oxides, transparent conductors, piezoelectric materials, battery electrode materials, electrochromic devices, optical filters, laser-active media, wide-bandgap semiconductors, solar absorbers, and many others. Keywords: metal enolates; metal oxides; mixed metal oxides; metal β-diketonates; main-group elements; rare earth metal elements; deposition; gas-phase; wet chemistry
{"title":"Advances in Deposition of Transition‐Metal Oxides from Metal Enolates","authors":"H. Lang, David Adner, C. Georgi","doi":"10.1002/9780470682531.PAT0910","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0910","url":null,"abstract":"This chapter is an update of part of a review published by our group elsewhere in Patai's Series; in addition, in this volume, chapters present the recent advances in the deposition of metals and oxides of main-group metals and rare-earth elements, all derived from metal enolates. \u0000 \u0000 \u0000 \u0000Metal oxides are essential as common inorganic crude materials, possessing a manifold portfolio of applications because of their singular physical and chemical properties. Metal oxides are formed by straight vaporization from metal oxide sources, by evaporation of metals in an oxidizing atmosphere, or via wet chemistry, for example, the sol-gel process. Their industrial use includes protective coatings, electrical insulator materials, gate oxides, transparent conductors, piezoelectric materials, battery electrode materials, electrochromic devices, optical filters, laser-active media, wide-bandgap semiconductors, solar absorbers, and many others. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metal enolates; \u0000metal oxides; \u0000mixed metal oxides; \u0000metal β-diketonates; \u0000main-group elements; \u0000rare earth metal elements; \u0000deposition; \u0000gas-phase; \u0000wet chemistry","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"221 1","pages":"1-38"},"PeriodicalIF":0.0,"publicationDate":"2016-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76643548","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 : 2016-06-21DOI: 10.1002/9780470682531.PAT0830
S. Slayden, J. Liebman
The current chapter discusses the chemical energetics of carbon-aluminum bonded species, both the “conventional” trivalent organoaluminum compounds such as monomeric Me3Al and its dimer and a variety of species of often surprising stoichiometry and structure. The study begins with the “simple” binary aluminum carbides, starting with AlC (neutral and ions). Incorporation of hydrogen leads to consideration of dimethylaluminum ionic compounds derived from the cationic [Me2Al]+ and anionic [Me2AlO]−. Methyldialuminum species with one Al–Al bond and at least one Al–C bond, ranging from [Al2Me]+ to [Al2Me7]−, are then examined. The experimental enthalpies of formation, vaporization and dimerization of trialkylalanes are tabulated. The most recent enthalpy of formation value for Et3Al is used to recommend slightly revised enthalpies of formation for trialkylalanes and the related alkylaluminum hydrides and halides. The interplay of aluminum and aromaticity is reviewed in the context of aluminum rich rings and clusters, relatively classical heterocycles such as aluminoles, and binding of neutral and cationic monoatomic Al with aromatics. The chapter closes with a discussion of aluminum halide complexes of benzene and cyclobutadiene derivatives. Keywords: aluminum carbide; trivalent organoaluminum compounds; monomers; dimers; neutral and related ions; dimethylaluminum species; methyldialuminum species; enthalpies of formation; enthalpies of vaporization; enthalpies of dimerization; alkylaluminum hydrides; alkylaluminum halides; aromaticity, rings and clusters; classical heterocycles; aluminum halide complexes
{"title":"Aspects of the Chemical Energetics of Carbon–Aluminum Bonded Species","authors":"S. Slayden, J. Liebman","doi":"10.1002/9780470682531.PAT0830","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0830","url":null,"abstract":"The current chapter discusses the chemical energetics of carbon-aluminum bonded species, both the “conventional” trivalent organoaluminum compounds such as monomeric Me3Al and its dimer and a variety of species of often surprising stoichiometry and structure. \u0000 \u0000 \u0000 \u0000The study begins with the “simple” binary aluminum carbides, starting with AlC (neutral and ions). Incorporation of hydrogen leads to consideration of dimethylaluminum ionic compounds derived from the cationic [Me2Al]+ and anionic [Me2AlO]−. \u0000 \u0000 \u0000 \u0000Methyldialuminum species with one Al–Al bond and at least one Al–C bond, ranging from [Al2Me]+ to [Al2Me7]−, are then examined. \u0000 \u0000 \u0000 \u0000The experimental enthalpies of formation, vaporization and dimerization of trialkylalanes are tabulated. The most recent enthalpy of formation value for Et3Al is used to recommend slightly revised enthalpies of formation for trialkylalanes and the related alkylaluminum hydrides and halides. \u0000 \u0000 \u0000 \u0000The interplay of aluminum and aromaticity is reviewed in the context of aluminum rich rings and clusters, relatively classical heterocycles such as aluminoles, and binding of neutral and cationic monoatomic Al with aromatics. \u0000 \u0000 \u0000 \u0000The chapter closes with a discussion of aluminum halide complexes of benzene and cyclobutadiene derivatives. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aluminum carbide; \u0000trivalent organoaluminum compounds; \u0000monomers; \u0000dimers; \u0000neutral and related ions; \u0000dimethylaluminum species; \u0000methyldialuminum species; \u0000enthalpies of formation; \u0000enthalpies of vaporization; \u0000enthalpies of dimerization; \u0000alkylaluminum hydrides; \u0000alkylaluminum halides; \u0000aromaticity, rings and clusters; \u0000classical heterocycles; \u0000aluminum halide complexes","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"162 1","pages":"1-38"},"PeriodicalIF":0.0,"publicationDate":"2016-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76989412","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 : 2016-06-21DOI: 10.1002/9780470682531.PAT0909
Shigehisa Akine
Various kinds of metal complexes having oligo(salen)-type ligands have been designed, synthesized, and characterized. Convergent arrangement of two or more metallosalen units contributes to the programmed formation of multi-metal structures. The oligo(salen) compounds are classified into three types: macrocyclic, acyclic (helical), and cage-like systems. In the macrocyclic systems, the metalation of the salen moieties significantly enhances the guest ion binding in the cavity. This enables the controlled synthesis of homo- and heterometallic cluster-like structures. In the acyclic systems, the metalation makes the ligand molecules adopt a helical conformation. These helical structures provided a new binding site, at which guest ions are recognized based on metal exchange protocol. The dynamic feature of the helical structures is utilized for stimuli-responsive systems that can change the helicity upon binding with chemical species. Metal complexes obtained from cage-like oligo(salen) ligands have a three-dimensional cavity suitable for size-selective guest recognition. The cooperative metal binding by taking advantage of the convergent oligo(salen) structures discussed in this chapter will be useful to achieve sophisticated responsive functions, which are based on the intrinsic properties and the dynamic structural conversions of the multimetallic core of the complexes. Keywords: salen; host-guest chemistry; ion recognition; metallohost; macrocycle; helical structure; helicity control; molecular cage; cooperative effect; template synthesis
{"title":"Metal Complexes with Oligo(Salen)‐Type Ligands","authors":"Shigehisa Akine","doi":"10.1002/9780470682531.PAT0909","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0909","url":null,"abstract":"Various kinds of metal complexes having oligo(salen)-type ligands have been designed, synthesized, and characterized. Convergent arrangement of two or more metallosalen units contributes to the programmed formation of multi-metal structures. The oligo(salen) compounds are classified into three types: macrocyclic, acyclic (helical), and cage-like systems. In the macrocyclic systems, the metalation of the salen moieties significantly enhances the guest ion binding in the cavity. This enables the controlled synthesis of homo- and heterometallic cluster-like structures. In the acyclic systems, the metalation makes the ligand molecules adopt a helical conformation. These helical structures provided a new binding site, at which guest ions are recognized based on metal exchange protocol. The dynamic feature of the helical structures is utilized for stimuli-responsive systems that can change the helicity upon binding with chemical species. Metal complexes obtained from cage-like oligo(salen) ligands have a three-dimensional cavity suitable for size-selective guest recognition. The cooperative metal binding by taking advantage of the convergent oligo(salen) structures discussed in this chapter will be useful to achieve sophisticated responsive functions, which are based on the intrinsic properties and the dynamic structural conversions of the multimetallic core of the complexes. \u0000 \u0000 \u0000Keywords: \u0000 \u0000salen; \u0000host-guest chemistry; \u0000ion recognition; \u0000metallohost; \u0000macrocycle; \u0000helical structure; \u0000helicity control; \u0000molecular cage; \u0000cooperative effect; \u0000template synthesis","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"117 1","pages":"1-42"},"PeriodicalIF":0.0,"publicationDate":"2016-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73152456","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 : 2016-06-21DOI: 10.1002/9780470682531.PAT0911
H. Lang, David Adner, C. Georgi
This chapter is an update of a review published by our group elsewhere in Patai's Series; in addition, in this volume, chapters present the recent advances in the deposition of metals and transition-metal oxides, all derived from metal enolates. Materials featuring group 3 - 12 elements have attracted great technological and scientific attention during the last decades because of their outstanding chemical and physical properties. They are widely used in industry, including a variety of catalyst supports, coatings, as dielectrics for semiconducting devices, and as sensors. Keywords: metal enolates; transition-metal oxides; β-diketonates; β-enaminones; β-diketiminates; macrocycles; deposition; gas phase; wet chemistry; group 3 - 12 elements
{"title":"Advances in Deposition of Main-Group Metal Oxides and Rare-Earth Oxides from Metal Enolates","authors":"H. Lang, David Adner, C. Georgi","doi":"10.1002/9780470682531.PAT0911","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0911","url":null,"abstract":"This chapter is an update of a review published by our group elsewhere in Patai's Series; in addition, in this volume, chapters present the recent advances in the deposition of metals and transition-metal oxides, all derived from metal enolates. \u0000 \u0000 \u0000 \u0000Materials featuring group 3 - 12 elements have attracted great technological and scientific attention during the last decades because of their outstanding chemical and physical properties. They are widely used in industry, including a variety of catalyst supports, coatings, as dielectrics for semiconducting devices, and as sensors. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metal enolates; \u0000transition-metal oxides; \u0000β-diketonates; \u0000β-enaminones; \u0000β-diketiminates; \u0000macrocycles; \u0000deposition; \u0000gas phase; \u0000wet chemistry; \u0000group 3 - 12 elements","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"1203 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2016-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86485681","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 : 2016-04-06DOI: 10.1002/9780470682531.PAT0905
P. Deplano, D. Espa, L. Pilia
{"title":"Recent Advances in the Structure and Properties of Metal–Dithiolene Complexes","authors":"P. Deplano, D. Espa, L. Pilia","doi":"10.1002/9780470682531.PAT0905","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0905","url":null,"abstract":"","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"77 1","pages":"1-31"},"PeriodicalIF":0.0,"publicationDate":"2016-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82829260","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 : 2016-03-31DOI: 10.1002/9780470682531.PAT0901
H. Lang, David Adner, C. Georgi
This chapter describes the use of metal enolates as precursors for the deposition and growth of nano-sized materials of a large variety of metal, mixed metal-metal oxide, and alloy layers and patterns, an area that has rapidly developed during the last couple of decades. As metal enolates, mostly mononuclear main group, transition metal, and rare earth metal complexes featuring various β-diketonate or β-ketoiminate ligands have been used. Based on their intrinsic properties, for example, reactivity, transparency, conductivity, and magnetism, a large variety of metal and/or metal oxide deposits are available at present. As deposition processes, mainly gas-phase (e.g., CVD2–9 and ALD8–19) or liquid-phase procedures (including spin-coating, dip-coating, sol–gel, and printing techniques) were used. Controlled decomposition of the appropriate metal enolates allows the generation of diverse metal and metal oxide materials, for example, dense or porous thin layers and nanomaterials in the form of particles, dots, rods, tubes, and wires. Where appropriate, the similarities and differences, including elementary decomposition steps that are common for the respective metal enolate precursors, are discussed as well. Keywords: metal enolates; mixed metal oxides; organometallic and metalorganic iridium compounds; nickel enolates; platinum-group metal ruthenium; transition-metal β-diketonates
{"title":"Advances in Deposition of Metals from Metal Enolates","authors":"H. Lang, David Adner, C. Georgi","doi":"10.1002/9780470682531.PAT0901","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0901","url":null,"abstract":"This chapter describes the use of metal enolates as precursors for the deposition and growth of nano-sized materials of a large variety of metal, mixed metal-metal oxide, and alloy layers and patterns, an area that has rapidly developed during the last couple of decades. As metal enolates, mostly mononuclear main group, transition metal, and rare earth metal complexes featuring various β-diketonate or β-ketoiminate ligands have been used. Based on their intrinsic properties, for example, reactivity, transparency, conductivity, and magnetism, a large variety of metal and/or metal oxide deposits are available at present. As deposition processes, mainly gas-phase (e.g., CVD2–9 and ALD8–19) or liquid-phase procedures (including spin-coating, dip-coating, sol–gel, and printing techniques) were used. Controlled decomposition of the appropriate metal enolates allows the generation of diverse metal and metal oxide materials, for example, dense or porous thin layers and nanomaterials in the form of particles, dots, rods, tubes, and wires. Where appropriate, the similarities and differences, including elementary decomposition steps that are common for the respective metal enolate precursors, are discussed as well. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metal enolates; \u0000mixed metal oxides; \u0000organometallic and metalorganic iridium compounds; \u0000nickel enolates; \u0000platinum-group metal ruthenium; \u0000transition-metal β-diketonates","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"83 1","pages":"1-28"},"PeriodicalIF":0.0,"publicationDate":"2016-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84259910","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 : 2016-03-31DOI: 10.1002/9780470682531.PAT0840
C. Martineau, F. Taulelle, M. Haouas
Use of 27Al nuclear magnetic resonance (NMR) spectroscopy for the study of the chemistry of aluminum in a variety of compounds during the last 25 years is reported. A compilation of NMR data, including chemical shifts and heteronuclear scalar couplings, is provided for a wide range of families of aluminum compounds in both solution and solid state. Recent methodological and technological advances in the field of quadrupolar NMR are detailed and their applications to 27Al nucleus are illustrated. The potential of this technique is exemplified with some representative studies of relevance to mineral, biological, and organic aluminum-based systems. Keywords: 27Al nucleus; aluminum chemistry; chemical shifts; materials; nuclear magnetic resonance; organoaluminum; quadrupolar relaxation; scalar coupling; spectroscopy
{"title":"The Use of 27Al NMR to Study Aluminum Compounds: A Survey of the Last 25 Years","authors":"C. Martineau, F. Taulelle, M. Haouas","doi":"10.1002/9780470682531.PAT0840","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0840","url":null,"abstract":"Use of 27Al nuclear magnetic resonance (NMR) spectroscopy for the study of the chemistry of aluminum in a variety of compounds during the last 25 years is reported. A compilation of NMR data, including chemical shifts and heteronuclear scalar couplings, is provided for a wide range of families of aluminum compounds in both solution and solid state. Recent methodological and technological advances in the field of quadrupolar NMR are detailed and their applications to 27Al nucleus are illustrated. The potential of this technique is exemplified with some representative studies of relevance to mineral, biological, and organic aluminum-based systems. \u0000 \u0000 \u0000Keywords: \u0000 \u000027Al nucleus; \u0000aluminum chemistry; \u0000chemical shifts; \u0000materials; \u0000nuclear magnetic resonance; \u0000organoaluminum; \u0000quadrupolar relaxation; \u0000scalar coupling; \u0000spectroscopy","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"20 1","pages":"1-51"},"PeriodicalIF":0.0,"publicationDate":"2016-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80318284","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 : 2016-03-31DOI: 10.1002/9780470682531.PAT0906
J. Zabicky
The chapter is an update of one published in 2009, covering the literature up to the autumn of 2014. Due to space limitations assigned to chapters in this book, the review of analytical methods was divided into two parts, the companion of this chapter dealing with electrochemical methods of analysis and the present one dealing with all the rest, especially spectrophotometric and optical methods. The same guidelines as in the older chapter were followed for the selection of analytical methods, namely: A section dealing with detection and determination of specific metal enolates, a section dealing with conversion of metal cation analytes into complexes with enolic ligands before end analysis and a section presenting the use of certain metal enolates as analytical aids and tools. Keywords: chromatography; chromogenic sensors; extraction; fluorogenic sensors; metal-enol complexes; metal enolate analysis; optodes
{"title":"Recent Advances in Nonelectrochemical Analytical Methods Involving Metal Enolates","authors":"J. Zabicky","doi":"10.1002/9780470682531.PAT0906","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0906","url":null,"abstract":"The chapter is an update of one published in 2009, covering the literature up to the autumn of 2014. Due to space limitations assigned to chapters in this book, the review of analytical methods was divided into two parts, the companion of this chapter dealing with electrochemical methods of analysis and the present one dealing with all the rest, especially spectrophotometric and optical methods. The same guidelines as in the older chapter were followed for the selection of analytical methods, namely: A section dealing with detection and determination of specific metal enolates, a section dealing with conversion of metal cation analytes into complexes with enolic ligands before end analysis and a section presenting the use of certain metal enolates as analytical aids and tools. \u0000 \u0000 \u0000Keywords: \u0000 \u0000chromatography; \u0000chromogenic sensors; \u0000extraction; \u0000fluorogenic sensors; \u0000metal-enol complexes; \u0000metal enolate analysis; \u0000optodes","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2016-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85606900","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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