bluuebunny/crossref_metadata_2025_split huggingface dataset:
Alkali Metals: Organometallic ChemistryBased in part on the article Alkali Metals: Organometallic Chemistry by Charles M. Lukehart which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Harvey Melanie J. 
Published: March 2006

Abstract
Organolithium complexes, like the organomagnesium Grignard Reagents, are important reactants in organic synthesis. The similarity in structure, bonding, and reactivity of organolithium and ‐magnesium compounds exemplifies the common chemistry exhibited by representative elements that appear in the same diagonal in the periodic table. Although much debate exists over the degree of covalency within lithium – carbon‐bonding interactions, the presence of some covalent character in LiC bonds of alkyllithium compounds is widely accepted. The bonding interactions within organoalkali metal complexes of the heavier alkali metals are generally considered to be strongly electrostatic or ionic in nature. This is supported by a large collection of evidence, consisting primarily of solution NMR data, single‐crystal X‐ray analyses, and gas‐phase computational studies. Many of the organolithium compounds are soluble in hydrocarbons, but organometallic compounds of the heavier group 1 metals generally require more polar solvents. In general, the reactivity of the alkali metals and the reactivity of the organometallic compounds of these metals increase as we go down the group or column. Organoalkali metal compounds are similar to, but more reactive than Grignard reagents. Organoalkali metal compounds are both air‐ and moisture‐sensitive and are sometimes pyrophoric. In addition, organoalkali metal compounds will react as Brønsted bases with protic reagents. Specific details regarding the synthesis, reactivity, and structures of various types of organoalkali metal compounds will be discussed.
Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Saulys Dovas A. , Hill E. Alexander 
Published: March 2006

AbstractVictor Grignard found in 1900 that solutions of organomagnesium halides form easily in the reaction of an organic halide with magnesium metal in diethyl ether. These Grignard reagents undergo useful reactions with many kinds of substrates. This discovery ushered in a new era in organometallic chemistry and provided chemists with a powerful and versatile reagent for synthesis of a wide variety of organic and organometallic compounds. This article discusses Grignard reagents in the broader context of organomagnesium chemistry. Preparatory methods surveyed include direct reaction of organic halides with the metal, exchange reactions with other organometallic compounds, as well as carbo‐ and hydrometalations. The current level of understanding of the mechanism of Grignard formation is summarized. The formation and reactivity of unusual species such as cluster Grignard reagents, for example, RMg4X (R = organic group, and X = halide) and polymagnesium compounds, for example, Ru[C5(MgCl)5]2are also discussed. The bonding and structure of organomagnesium compounds (as well as that of beryllium analogues) as described by diffraction methods, thermochemical data, colligative properties, spectroscopic (vibrational, nuclear magnetic, and electronic) measurements, kinetic studies, mass spectrometry, and theoretical methods are outlined.The most prominent chemical property of organomagnesium compounds is their ability to deliver an effectively ‘anionic’ organic group with nucleophilic properties. As alkylating reagents, their important reactions include nucleophilic displacement of less basic leaving groups from saturated carbon atoms or other elements, addition to carbonyl groups and other unsaturated functions, and nucleophilic substitution at the acyl group of carboxylic acid derivatives. This broad array of substrates is surveyed, as are the effects of solvents and catalysts on reactivity. Less conspicuous reactions with wholly or predominantly inorganic substrates are also considered. Electron transfer reactions where organomagnesium compounds act as reductants are discussed.Organoberyllium compounds are more difficult to prepare and are less nucleophilic than their magnesium counterparts. These features, together with their high toxicity, have limited their utility. Methods of preparation, as well as descriptions of bonding, structure, and reactivity patterns are presented. Of special note are recent advances in cyclopentadienyl beryllium chemistry, as well as the advent of beryllium–silicon chemistry.
Bismuth: Organometallic Chemistry
Authors: Whitmire Kenton H. 
Published: March 2006

Abstract
Bismuth readily forms a variety of tri‐ and pentavalent organic derivatives by the reactions of bismuth halides with Grignard, organolithium, organozinc, or organoaluminum reagents. Bismuth(III) triaryl compounds are readily oxidized by chlorine and bromine to triaryl dihalides, while iodine reacts to produce aryl bismuth iodides. Some organobismuth compounds are Lewis acidic, showing the ready formation of higher coordination number adducts with traditional ligands. A variety of organobismuth compounds with bismuth–bismuth and bismuth–transition metal bonds are described. Organobismuth(V) have found uses as selective oxidants and aryl transfer reagents.
Boron: Polyhedral CarboranesBased in part on the article Boron: Polyhedral Carboranes by Robert E. Williams which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Hosmane Narayan S. , Maguire John A. 
Published: March 2006

Abstract
Carboranes are compounds in which carbon, boron, and hydrogen atoms are present in polyhedral cages. The cages are stabilized by multi‐centered bonds, which gives the carboranes unique chemical and structural properties. Many of these compounds are chemically and thermally stable enough to allow their use as boron delivery agent for boron neutron capture therapy (BNCT) in cancer treatment and as molecular assemblies.
Carbon: Fullerenes
Authors: Crane Jonathan D. , Kroto Harold W. 
Published: March 2006

Abstract
The discovery of the fullerenes has revolutionalized the chemistry of carbon. For the first time a molecular form of the element carbon is available that can be manipulated and functionalized by the wide range of techniques available to molecular and materials scientists. In a very short space of time the fullerenes and their derivatives have been found to display many fascinating physical and chemical properties, and the astonishing pace of development in fullerene research is ample testimony to their great potential.
Carbon: Inorganic ChemistryBased in part on the article Carbon: Inorganic Chemistry by R. Bruce King which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Friščić Tomislav , MacGillivray Leonard R. 
Published: March 2006

Abstract
The article provides a brief and general overview of the chemical and physical properties of carbon, as it relates to inorganic chemistry. Several allotropic forms of carbon are described, with general properties discussed. The characteristics and synthetic methods for the preparation of simple compounds involving carbon or carbon and hydrogen with halogens, oxygen, sulfur, as well as nitrogen, are provided. In addition, recent developments in supramolecular chemistry to construct ladder‐like carbon frameworks are outlined.
Chalcogenides: Solid‐State ChemistryBased in part on the article Chalcogenides: Solid State Chemistry by Patricia M. Keane which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Kanatzidis Mercouri G. 
Published: March 2006

AbstractThis article deals with the solid‐state chemistry of chalcogenides and describes mainly the developments during the past decade. The article is not exhaustive but is meant to give a broad set of examples of interesting compounds and solid‐state chemistry of these compounds so that the reader can obtain a reasonable and rounded view of the recent activities in this area. Further depth and additional information can be obtained from the available references.
Chlorine, Bromine, Iodine, & Astatine: Inorganic ChemistryBased in part on the article Chlorine, Bromine, Iodine, & Astatine: Inorganic Chemistry by Jacob Shamir which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Lang Jian‐Ping 
Published: March 2006

AbstractThis chapter summarizes the occurrences, atomic structures, and molecular properties of the elements of group 17, chlorine, bromine, iodine, and astatine. The charge‐transfer complexes of halogens with different inorganic or organic compounds are outlined. The interhalogen compounds, especially those of polyiodides, are discussed with respect to their preparation and their structure varieties. The halogen oxides such as halogen oxide cations, halogen oxide fluorides, oxoacids and oxoacid salts, and halogen derivatives of oxoacids are discussed. Finally, organic polyvalent halogen derivatives, mainly including those of iodine (I), iodine (III), and iodine (V), are mentioned.
Cobalt: Organometallic ChemistryBased in part on the article Cobalt: Organometallic Chemistry by Ulrich Koelle which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Quisenberry Keith T. , Hanusa Timothy P. 
Published: March 2006

AbstractAmong the longest known families of organometallic compounds, those of cobalt display great diversity in their structures and oxidation states. The ligands accommodated in organocobalt compounds range from strong σ‐donors such as hydrides and alkyls, to π‐acid ligands such as carbonyls and phosphines. The carbonyl cluster compounds of cobalt are numerous and they play a major role in catalytic reactions of enormous industrial importance such as hydroformylation reactions (conversion of alkenes to aldehydes) and Pauson–Khand cycloaddition (production of cyclic ketones). Cobalt is an electron‐rich late transition metal, a property reflected throughout its organometallic chemistry. Thus, the carbonyl ‘hydride’ HCo(CO)4is actually a strong acid and does not have ‘hydridic’ (H−) properties. Similarly, cobalt does not complex to any group 15 or 16 heterocycles such as pyridine or thiophene. In contrast, boracycles are good ligands for cobalt in a sandwich complex because an electropositive atom such as boron incorporated in a π‐cyclic ring stabilizes the electron‐rich central metal. The cyclopentadienyl ligand is found extensively throughout organocobalt chemistry – not only in cobaltocenes, but also in half‐sandwich complexes of the type (C5H5)CoL2, where L is CO, alkene, alkyne, or phosphine. The (C5H5)CoL2complexes are useful in alkyne dimerization and trimerization. Cobaltocene itself ((C5H5)2Co) is easily oxidized to the extraordinarily stable 18‐electron cobaltocenium cation, [(C5H5)2Co]+. Cobalt can be incorporated into carborane cages, which have been found to be efficient extractors of radioactive metal ions such as90Sr and137Cs in water at low pH. Cobalamins, which consist of a cobalt central atom in a substituted corrin ring, are examples of naturally occurring organometallic compounds, and coenzyme B12was the first recognized example of a biological organometallic compound. Methylcobalamins play a role in biology, where they are found in microorganisms and can methylate mercury in the environment.
Coordination Chemistry: History
Authors: Kauffman George B. 
Published: March 2006

Abstract
This article discusses a chronological history of the major discoveries, both theoretical and experimental, of coordination chemistry from antiquity through 2003. In view of Alfred Werner's central role in the field, considerable space is allotted to his achievements, but contributions of lesser‐known pioneers are also included. Some of the most historically significant coordination compounds are first discussed, along with several pre‐Werner theories of their formation, constitution, and configuration, followed by Werner's theory and his most important discoveries.
Copper Proteins with Type 1 SitesBased in part on the article Copper Proteins with Type 1 Sites by Edward N. Baker which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Hart P. John , Nersissian Aram. M. , George Serena DeBeer 
Published: March 2006

Abstract

Copper Proteins with Type 1
Sites is a general review that focuses on single‐domain proteins that bind ‘blue’ or ‘type 1’ copper. Larger, multidomain proteins that contain type 1 copper in addition to other types of copper centers are not discussed at any length in this article. Blue copper proteins are so named because in solution they are a brilliant blue/azure color when the copper ion is in its Cu(II) oxidation state. The bright blue color comes from a charge transfer (CT) between Cu(II) and the sulfur (thiolate) of a ligating cysteine residue. Because of this intense color, type 1 copper proteins were among the first to be isolated because they could be tracked easily during purification processes. This, together with their unique spectroscopic properties that have no parallel in small‐molecule copper complexes, has made them the subject of intense study over the last 35 years. This article focuses on three main aspects of type 1 copper proteins: (1) their occurrence, distribution, and classification based on analyses of genomic and expressed sequence tag data; (2) their three‐dimensional structures as determined by the well‐established tools of single‐crystal X‐ray diffraction and nuclear magnetic resonance (NMR); and (3) their electronic, spectroscopic, and electron‐transfer properties.
Decarbonylation Catalysis
Authors: Jardine Fred H. 
Published: March 2006

Abstract
Aldehydes or acid chlorides can be decarbonylated to alkanes or alkenes respectively by rhodium complexes. However, α,ω‐alkenals frequently isomerize to cyclic ketones. Palladium complexes decarbonylate aroyl cyanides. Stoichiometric reactions occur with many carbonyl compounds at low temperatures. Above 150°C, several of the reactions are catalytic. Aldehyde tautomers such as allylic alcohols or carbohydrates are also decarbonylated.
Dinuclear Organometallic Cluster Complexes
Authors: Kiss Gabor , McDonough James Eric , Weir John J. , Hoff Carl D. 
Published: March 2006

AbstractMetal–metal bonding in dinuclear complexes plays a key role in inorganic and organometallic chemistry. It is the basis for development of polymers and clusters derived from this simple unit. Its chemistry now approaches the ‘functional group’ status, typically used in organic chemistry for classes of compounds. However, owing to the array of metals and oxidation states involved, a wide range of structures, reactions, and properties are observed for this important class of compounds. This article introduces the topic of metal–metal bonded complexes and attempts to outline the synthetic strategies used to prepare metal–metal bonded complexes, some of their characteristic properties and reactions, as well as to provide a brief introduction to historical development and emerging directions of this central area of inorganic chemistry.
Electron Transfer Reactions: TheoryBased in part on the article Electron Transfer Reactions: Theory by Roderick D. Cannon which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Matyushov Dmitry 
Published: March 2006

Abstract
This article discusses the progress in the field of electron‐transfer theory over the period of about 50 years since early 50s marked by the development of theories of radiationless transitions in molecules in the gas phase and the Marcus theory of electronic transitions between ions in solution. The article starts with the classification of electron‐transfer reactions in terms of reaction mechanisms and the extent of electronic delocalization. This is followed by the outline of the picture of intersecting parabolas due to Marcus, which defines the activation barrier for nonadiabatic electron transfer. The rate of nonadiabatic electron transfer strongly depends on electronic coupling between the donor and acceptor states. The Mulliken‐Hush theory, along with its recent generalizations, provides coupling from spectroscopic observables. The success of electron‐transfer theories has largely been supported by the connection between thermal rates and optical spectroscopy. The activation barrier can be obtained from optical spectra by using the band‐shape analysis discussed next. This is followed by the overview of the inverted region of electron transfer and the consequences of introducing nonparabolic free energy surfaces of electron transfer in polarizable systems. The advent of ultrafast spectroscopic techniques opened up a new avenue in electron‐transfer research related to the effects of polarization dynamics on the reaction rate. Measurements at varying pressure allow one to introduce an additional thermodynamic variable probing the activation barrier. The article concludes with a brief account of magnetic effects in electron transfer.
Electronic Structure of Main‐Group CompoundsBased in part on the article Electronic Structure of Main Group Compounds by Jeremy K. Burdett which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Frenking Gernot , Lein Matthias 
Published: March 2006

AbstractQuantum chemical research has made significant progress in the understanding of the electronic structure and the nature of the interatomic interactions yielding chemical bonds in molecules. Ad hoc models of chemical bonding have been complemented or replaced by more sophisticated approaches for analyzing the bonding situation in molecules. The new methods build a well‐defined bridge between the heuristic bonding models using pictorial approaches and the physical mechanism of a chemical bond. Bonding models can be examined with quantum chemical methods, which show that chemical intuition and physics do not exclude each other. The paper describes important methods using charge and energy partitioning approaches, which are helpful and widely used in modern theoretical inorganic chemistry for understanding the electronic structure and bonding situation of main‐group compounds. The application of the methods to representative main‐group compounds is described and the results are critically discussed.
Germanium: Inorganic ChemistryBased in part on the article Germanium: Inorganic Chemistry by Frank Glockling which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.
Authors: Qin Chao , Gao Lei , Wang Enbo 
Published: March 2006

AbstractIn this article, the basic physical and chemical properties, preparation, and applications of germanium and its related compounds are all described in detail. The whole chapter is divided into 12 sections, namely, introduction, analysis, the element, hydrides, boron derivatives, nitrogen compounds, phosphorus and arsenic compounds, oxygen‐bonded compounds, sulfides, selenides and tellurides, halides, metalloid‐ and metal‐bonded compounds, and polyoxometalates of germanium. In each section, some new development in the synthesis and applications of new compounds are included following the fundamental information.In the introduction section, the discovery, distribution, effect on organisms, basic chemistry, and application of germanium are given briefly.The analysis section gives a concise description of the main analysis processes.The preparation, basic physical and chemical properties of metal germanium, and anionic germanium clusters are included in the element section.In the following sections, different germanium compounds are described mainly according to the different valence germanium exhibits. Their fundamental synthetic routes, discovery and synthesis of new compounds, and the new development in the related fields are emphasized. In particular, contents concerning the construction of framework materials, the synthesis of polyoxometalates, which represent the tendency of development in inorganic chemistry, are presented comprehensively.More than seventy equations are used to illustrate certain reactions, and detailed information of some important compounds and their synthetic routes are also given in the form of structures, schemes, and figures. Certain data, properties and structure information of germanium, and its compounds are listed in some tables.Related articles are also given following the main content with the details explained in the text.This article containing extensive contents about germanium should provide a basic resource for reference of the related studies. An explanation of the development of the recent germanium chemistry may provide insight into the exploration of new fields.
Gold: Inorganic & Coordination Chemistry
Authors: Vittal Jagadese J. , Puddephatt Richard J. 
Published: March 2006

Abstract
Gold compounds are finding new applications in catalysis, medicine, and molecular materials, based on their reactivity and unusual physical and chemical properties. The theoretical basis of the unique properties of gold compounds continues to develop rapidly and provides a constant challenge for synthesis of new types of gold compounds. This chapter gives an overview of these exciting developments while giving an overview of the modern inorganic chemistry of gold.
Hydroboration CatalysisBased in part on the article Hydroboration Catalysis by Kevin Burgess & Wilfred A. van der Donk which appeared in the
Encyclopedia of Inorganic Chemistry, First Edition
.
Authors: Vogels Christopher M. , Westcott Stephen A. 
Published: March 2006

Abstract
Among the most significant advances in organic synthesis over the past few decades are those associated with the development of transition metal complexes for their use as catalysts in organic reactions. The discovery that transition metals can also be used to catalyze the addition of BH bonds to unsaturated substrates has provided the synthetic chemist with another valuable tool. This review examines recent advances in the field of catalyzed hydroborations and their applications in organic synthesis.
Indium: Organometallic Chemistry
Authors: Kumar Banger Kulbinder 
Published: March 2006

AbstractAn overview of the chemistry of organoindium compounds containing at least one InC bond over the last ten years is reported in detail. In particular, the synthesis, characterization, properties of homoleptic and heteroleptic organoindium derivatives, organoindium(0), (I), and (II) compounds, and in addition anionic compounds are also reported. Furthermore, the use of organoindium compounds for thin film, nanotechnology, and organic synthesis is discussed.
Ionic Conductors
Authors: Greenblatt Martha 
Published: March 2006

AbstractThe fundamental structural and physical properties of ionic conductors in the solid state are briefly discussed. Recent developments in ionically conducting solids are reviewed. Materials discussed include: crystalline cation conductors with Na+, Li+, and H+ion motion; crystalline anion conductors, primarily with the fluorite‐type structure and with oxide‐ and fluoride ion mobilities; mixed ionic/electronic conductors; amorphous glass electrolytes and polymer solid electrolytes. Applications of some of these solid‐state ionic conductors in electrochemical devices such as sodium and lithium rechargeable batteries, sensors, fuel cells and electrochromic smart windows are presented.