Patai's Chemistry of Functional Groups最新文献_第9页

The Chemistry of Gold–Metal Bonds 金-金属键的化学性质

Patai's Chemistry of Functional Groups Pub Date : 2015-03-25 DOI: 10.1002/9780470682531.PAT0815

C. Silvestru, A. Laguna

{"title":"The Chemistry of Gold–Metal Bonds","authors":"C. Silvestru, A. Laguna","doi":"10.1002/9780470682531.PAT0815","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0815","url":null,"abstract":"This chapter summarizes the preparation, structural characterization and properties of heterometallic gold compounds built through metal–metal interactions or bonds. They are mainly synthesized following four different strategies. Two of them use the acid-base process with gold precursors acting as acids or organoaurates acting as bases, the third one consists of the use of bidentate bridging ligands, and the fourth uses the isolobal relationship between the [(R3P)Au]+ cations and the proton in carbonyl clusters. The structural behavior of these complexes has been studied by different methods, mainly Mossbauer spectroscopy, nuclear magnetic resonance spectroscopy, and single-crystal X-ray diffraction. Their structures show discrete molecules, extended linear chains or even two- or three-dimensional networks. Many of these complexes display luminescence and the emissions are strongly dependent on their structures. Some theoretical calculations are able to show that the formation of metal–metal interactions or bonds, as well as the gold environments, are the main aspects that affect the energy of the emissions. Other very promising areas of research such as the potential applications in electrochemistry, in biology (antiproliferative and antitumoral activity) or as homogeneous and heterogeneous catalysts are also discussed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000biological properties; \u0000catalysis; \u0000heterometallic gold complexes; \u0000luminescence; \u0000metal–gold bonds; \u0000metal–gold clusters; \u0000metal–gold interactions; \u0000silver complexes; \u0000thallium complexes","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"95 1","pages":"1-118"},"PeriodicalIF":0.0,"publicationDate":"2015-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88200141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 5

1,1-Dihydroperoxides 1,1-Dihydroperoxides

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0871

Chris Schwartz, P. Dussault

{"title":"1,1-Dihydroperoxides","authors":"Chris Schwartz, P. Dussault","doi":"10.1002/9780470682531.PAT0871","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0871","url":null,"abstract":"Gem-dihydroperoxides (g-DHPs), often referred to as 1,1-dihydroperoxides, are a class of molecules of interest because of their reactivity as well as their utility as synthetic reagents and intermediates. This review begins with a listing of previous reviews and commercially available g-DHPs, followed by a brief discussion of safety and regulatory issues. The properties of g-DHPs are then overviewed, with an emphasis on the physical properties, biological activity, thermal stability, spectroscopic properties, and behavior on chromatographic media. The remaining sections describe the synthesis and reactions of g-DHPS. The largest of these sections describes the various methods for synthesis of g-DHPs based upon class of catalyst or reagent and compares applications of different reagents selected target skeletons. One of the most significant applications of g-DHPs, their use as precursors for 1,2,4,5-tetraoxanes, is discussed in detail, including tabular comparisons of approaches to selected skeletons. The chapter concludes with a discussion of other important reactions of g-DHPs, including alkylations, nucleophilic and electrophile-promoted additions to alkenes, acetalizations, acylations and acylation-promoted fragmentations, acid-promoted dimerizations and decompositions, silylations, and application as oxygen transfer agents. \u0000 \u0000 \u0000Keywords: \u0000 \u0000cylation; \u0000alkylation; \u0000Bronsted acid; \u00001,1-dihydroperoxide; \u0000gem-dihydroperoxide; \u0000hydrogen peroxide; \u0000Lewis acid; \u0000synthesis; \u0000silylation; \u00001,2,4,5-tetraoxane","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"25 1","pages":"1-38"},"PeriodicalIF":0.0,"publicationDate":"2014-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79280837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 2

Theory of Gold‐Mediated Reactions: From Single Metal Site to Cluster 金介导的反应理论:从单一金属位点到簇

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0805

Hui Chen, Yi Gao

{"title":"Theory of Gold‐Mediated Reactions: From Single Metal Site to Cluster","authors":"Hui Chen, Yi Gao","doi":"10.1002/9780470682531.PAT0805","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0805","url":null,"abstract":"In recent years, gold-mediated reactions have attracted considerable interests and witnessed explosive developments. Along with this trend, corresponding theoretical modelings are playing increasingly important role in the mechanism study of gold-mediated reactions. In this chapter, we briefly discuss some recent advances in understanding of gold-mediated reactions from theoretical modeling. Relevant theoretical methods as well as some technical issues for computational treatment of heavy element gold are introduced. As a key point in many homogenous gold-mediated reactions that involve single metal site, substrate-gold interaction is examined from theoretical point of view. Then the mechanisms of some typical homogenous gold-mediated reactions are discussed. Concerning gold-mediated reactions involving more than single metal site, CO oxidation by gold nanoclusters is discussed, with focus on structures of gold clusters and influencing factors for catalytic activities towards CO oxidation. \u0000 \u0000 \u0000Keywords: \u0000 \u0000ab initio wave function theory method; \u0000cluster; \u0000density functional theory method; \u0000gold catalysis; \u0000homogenous catalysis; \u0000relativistic effects","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"65 1","pages":"1-30"},"PeriodicalIF":0.0,"publicationDate":"2014-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87064119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1

Gas‐Phase Ion Chemistry of Organic Peroxides 有机过氧化物的气相离子化学

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0878

S. Kato, S. Blanksby

{"title":"Gas‐Phase Ion Chemistry of Organic Peroxides","authors":"S. Kato, S. Blanksby","doi":"10.1002/9780470682531.PAT0878","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0878","url":null,"abstract":"Over the last 30 years, mass spectrometry and allied technologies have provided significant new insights into the intrinsic, gas phase properties of organic peroxides. In this chapter, the formation and interrogation of neutral peroxides, and their ionized analogues in the gas phase are discussed for several key classes of organic peroxides. Methods for the formation of intact, gas phase cations and anions from labile, often nonvolatile, peroxides using conventional and contemporary soft ionization techniques are described. Studies of the unimolecular dissociation of these ionized peroxides are shown to yield new understanding of energetics and bonding as well as providing diagnostic markers for the elucidation of molecular structure. The bimolecular chemistries of peroxides in the gas phase are considered in two categories: (i) reactions of ions with neutral peroxides; and (ii) the reactions of deprotonated organic hydroperoxides with neutral substrates. Advanced topics cover analytical applications of chemical ionization to the detection of peroxides and peroxyl radicals along with the synthesis of distonic peroxyl radical ions. Studies of the gas phase spectroscopy of organic peroxides that exploit the ionized forms of the peroxides are reviewed including negative-ion photoelectron spectroscopy, infrared multiple photon dissociation and action spectroscopy.","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"6 1","pages":"1-54"},"PeriodicalIF":0.0,"publicationDate":"2014-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76518810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Gold‐Promoted Sigmatropic Rearrangements 金-促进sigrotropic重排

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0810

G. Henrion, F. Gagosz

引用次数: 2

An Introduction to the Consequences of Spin and Bond Strength in the Chemistry of Diatomic Oxygen, Peroxides, and Related Species 介绍自旋和键强度在双原子氧、过氧化物和相关物质的化学反应中的影响

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0860

A. Greer, A. Balaban, J. Liebman

引用次数: 1

Copper Peroxide Bioinorganic Chemistry: From Metalloenzymes to Bioinspired Synthetic Systems 过氧化铜生物无机化学:从金属酶到生物合成系统

Patai's Chemistry of Functional Groups Pub Date : 2014-12-29 DOI: 10.1002/9780470682531.PAT0863

I. Garcia-Bosch, K. Karlin

{"title":"Copper Peroxide Bioinorganic Chemistry: From Metalloenzymes to Bioinspired Synthetic Systems","authors":"I. Garcia-Bosch, K. Karlin","doi":"10.1002/9780470682531.PAT0863","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0863","url":null,"abstract":"During the last few decades, copper-dioxygen chemistry has emerged as a new and very active field of (bio)inorganic relevance. Highlighted herein are the major findings, including the principles of dioxygen activation in metal-containing proteins along with characterization and reactivity of natural copper-peroxo systems which are derived from reaction of molecular oxygen with copper(I) active-site centers. Inspired by the varied array of copper proteins-enzymes which have been characterized, synthetic bioinorganic researchers have developed model systems which are amenable to facilitating the electron-transfer and atom-transfer chemistry which pervades dioxygen binding to copper complexes found in various oxidation states (+1 to +3). These studies have provided for new coordination chemistry of fundamental importance. In addition, significant contributions concerning the identity of biological or chemical reactive intermediates and insights into copper enzyme reaction mechanisms have been made. Taking advantage of this rich redox chemistry, synthetic methods combining copper and O2 (or H2O2) have been explored by organic/inorganic chemists, seeking to employ this earth abundant element to replace routes now usually carried out with precious (expensive/non-benign) metals, developing green, sustainable and selective oxidative processes. \u0000 \u0000 \u0000Keywords: \u0000 \u0000bioinspired systems; \u0000biosynthesis; \u0000copper-metalloproteins; \u0000dioxygen-reduction; \u0000organic catalysis; \u0000redox-chemistry","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"8 1","pages":"1-52"},"PeriodicalIF":0.0,"publicationDate":"2014-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74488288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 2

Peroxide intermediates of oxidation processes: Organic trioxides 氧化过程的过氧化物中间体:有机三氧化物

Patai's Chemistry of Functional Groups Pub Date : 2014-09-17 DOI: 10.1002/9780470682531.PAT0874

S. Khursan

引用次数: 1

Aurocarbons: Binary Gold Carbides, Binary Carbon Aurides and their Derivatives 碳碳化合物:二元金碳化物、二元碳碳化物及其衍生物

Patai's Chemistry of Functional Groups Pub Date : 2014-09-17 DOI: 10.1002/9780470682531.PAT0801

H. Perks, J. Liebman

{"title":"Aurocarbons: Binary Gold Carbides, Binary Carbon Aurides and their Derivatives","authors":"H. Perks, J. Liebman","doi":"10.1002/9780470682531.PAT0801","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0801","url":null,"abstract":"This chapter discusses diverse aurocarbons, organometallic species which in their simplest form, the first class, are composed of only carbon and gold: they may be understood as binary gold carbides, binary carbon aurides, and as hydrocarbons in which the hydrogens have been replaced by gold. Such species include the highly explosive solid C2Au2 and gas phase exohedral gold-fullerene complexes (C60)2Au+. The second class of aurocarbons are species of the first class in which ligands have been affixed to the gold atoms. This includes the stable C2Au2(P(C6H5)3)2 and the octahedral [C(AuL)6]2+ (L = phenyl(bis(p-tolyl)) phosphine, the latter isolable as the crystalline (BF4)− salt. The third class allows for the presence of “a few” hydrogens or other univalent groups and so includes salts of the anion [HCCCCAuCCCCAuCCCCH]2− and solutions of the cation [C6H5CC(AuP(C6H5)3)2]+. It is to be emphasized that there must be direct gold–carbon bonding and so the heterometallic cluster Rh10C2(CO)2[AuP(C6H5)3)4] is not an aurocarbon of any class even though it contains an allmetal polyhedron, ligated gold atoms, endohedral carbon atoms and a plethora of ligands. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aurocarbons; \u0000binary carbon aurides; \u0000binary gold carbides; \u0000cations and anions; \u0000classes of organometallic species; \u0000fullerenes; \u0000hydrocarbons; \u0000organogold complexes; \u0000phosphines ligand","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"112 1","pages":"1-10"},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80689234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Chemistry of Gold–Allene Complexes 金-烯配合物的化学性质

Patai's Chemistry of Functional Groups Pub Date : 2014-09-17 DOI: 10.1002/9780470682531.PAT0812

M. Muñoz, César Hurtado-Rodrigo

{"title":"The Chemistry of Gold–Allene Complexes","authors":"M. Muñoz, César Hurtado-Rodrigo","doi":"10.1002/9780470682531.PAT0812","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0812","url":null,"abstract":"In recent years, gold-electrophilic activation of allenes has unraveled a huge potential for new reactivities toward the synthesis of complex molecules with synthetic or biological importance. \u0000 \u0000 \u0000 \u0000Gold and allenes are a unique combination that has shown to be very versatile and give better reactivity, and in some cases is complementary to other metals. Coordination of gold to allenes is more complex than coordination to a simple olefin or alkyne, and several types of structures can be predicted depending on the atoms involved in the coordination. The nature of the gold–allene interaction defines the reactivity of these complexes, which can be modulated toward the desired product by slight changes in the catalysts or reaction conditions. \u0000 \u0000 \u0000 \u0000New reactions involving gold–allene complexes for the formation of carbon–heteroatom or carbon–carbon bond formation will be discussed in this chapter, including inter- and intramolecular examples of nucleophilic additions, and inter- and intramolecular cycloaddition and cycloisomerization reactions with alkenes, dienes, alkynes, and other allenes. \u0000 \u0000 \u0000Keywords: \u0000 \u0000allenes; \u0000carbene-gold; \u0000cycloadditions; \u0000cycloisomerizations; \u0000electrophilic-activation; \u0000gold; \u0000nucleophiles; \u0000vinyl-gold","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"32 1","pages":"1-64"},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80733604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1