Showing papers in "Chemical Reviews in 2009"

Synthesis of Conjugated Polymers for Organic Solar Cell Applications

Abstract: -phenylenevinylene)s L4. Fluorene-Based Conjugated Polymers L4.1. Fluorene-Based Copolymers ContainingElectron-Rich MoietiesM4.2. Fluorene-Based Copolymers ContainingElectron-Deficient MoietiesN4.3. Fluorene-Based Copolymers ContainingPhosphorescent ComplexesQ5. Carbazole-Based Conjugated Polymers R5.1. Poly(2,7-carbazole)-Based Polymers R5.2. Indolo[3,2-

Electro-Fenton process and related electrochemical technologies based on Fenton's reaction chemistry

Abstract: 2.2. Fenton’s Chemistry 6575 2.2.1. Origins 6575 2.2.2. Fenton Process 6575 2.3. Photo-Fenton Process 6577 3. H2O2 Electrogeneration for Water Treatment 6577 3.1. Fundamentals 6578 3.2. Cathode Materials 6579 3.3. Divided Cells 6580 3.4. Undivided Cells 6583 4. Electro-Fenton (EF) Process 6585 4.1. Origins 6585 4.2. Fundamentals of EF for Water Remediation 6586 4.2.1. Cell Configuration 6586 4.2.2. Cathodic Fe2+ Regeneration 6586 4.2.3. Anodic Generation of Heterogeneous Hydroxyl Radical 6587

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

Abstract: A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Nonviral Vectors for Gene Delivery

Abstract: The development of nonviral vectors for safe and efficient gene delivery has been gaining considerable attention recently. An ideal nonviral vector must protect the gene against degradation by nuclease in the extracellular matrix, internalize the plasma membrane, escape from the endosomal compartment, unpackage the gene at some point and have no detrimental effects. In comparison to viruses, nonviral vectors are relatively easy to synthesize, less immunogenic, low in cost, and have no limitation in the size of a gene that can be delivered. Significant progress has been made in the basic science and applications of various nonviral gene delivery vectors; however, the majority of nonviral approaches are still inefficient and often toxic. To this end, two nonviral gene delivery systems using either biodegradable poly(D,Llactide-co-glycolide) (PLG) nanoparticles or cell penetrating peptide (CPP) complexes have been designed and studied using A549 human lung epithelial cells. PLG nanoparticles were optimized for gene delivery by varying particle surface chemistry using different coating materials that adsorb to the particle surface during formation. A variety of cationic coating materials were studied and compared to more conventional surfactants used for PLG nanoparticle fabrication. Nanoparticles (~200 nm) efficiently encapsulated plasmids encoding for luciferase (80-90%) and slowly released the same for two weeks. After a delay, moderate levels of gene expression appeared at day 5 for certain positively charged PLG particles and gene expression was maintained for at least two weeks. In contrast, gene expression mediated by polyethyleneimine (PEI) ended at day 5. PLG particles were also significantly less

Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications

Abstract: Keywords: Fragmentation Chain-Transfer ; Self-Assembled Monolayers ; Walled Carbon Nanotubes ; Well-Defined Polymer ; Nitroxide-Mediated Polymerization ; Block-Copolymer Brushes ; Poly(Methyl Methacrylate) Brushes ; Transfer Raft Polymerization ; Quartz-Crystal Microbalance ; Poly(Acrylic Acid) Brushes Reference EPFL-REVIEW-148464doi:10.1021/cr900045aView record in Web of Science Record created on 2010-04-23, modified on 2017-05-10

Effect of ions on the structure of water: structure making and breaking.

Abstract: 4. Structure of Ionic Hydration Shells 1351 4.1. Results from Diffraction Experiments 1351 4.1.1. X-ray Diffraction 1351 4.1.2. Neutron Diffraction 1351 4.2. Results from Computer Simulations 1352 4.3. Results from Spectroscopic Measurements 1354 4.3.1. Vibrational Spectroscopic Measurements 1354 4.3.2. EXAFS Spectroscopy 1354 4.3.3. NMR Relaxation Studies 1355 4.3.4. Dielectric Relaxation Studies 1355 4.4. Summary of the Structure of Ionic Hydration Shells 1355

Palladium-Based Electrocatalysts for Alcohol Oxidation in Half Cells and in Direct Alcohol Fuel Cells

Abstract: Direct alcohol fuel cells (DAFCs) are attracting increasing interest as power sources for portable applications due to some unquestionable advantages over analogous devices fed with hydrogen.1 Alcohols, such as methanol, ethanol, ethylene glycol, and glycerol, exhibit high volumetric energy density, and their storage and transport are much easier as compared to hydrogen. On the other hand, the oxidation kinetics of any alcohol are much slower and still H2-fueled polymer electrolyte fuel cells (PEMFCs) exhibit superior electrical performance as compared to DAFCs with comparable electroactive surface areas.2,3 Increasing research efforts are therefore being carried out to design and develop more efficient anode electrocatalysts for DAFCs.

Natural product synthesis using multicomponent reaction strategies.

Abstract: The preparation of urea by Wöhler constituted a landmark achievement in organic chemistry, and it laid the ground for the early days of target-oriented organic synthesis.1 Since then, significant progress has been achieved in this discipline; many powerful single bond forming reactions and asymmetric variants have been developed. These discoveries have paved the way for the stereoselective assembly of complex organic molecules, a task deemed inconceivable by early practitioners. A great many strategies were invented by chemists in order to facilitate the synthesis of complex natural products.2 One avenue in emulating nature’s efficiency would * To whom correspondence should be addressed. E-mail: dennis.hall@ ualberta.ca. † Novartis Institute for Biomedical Research. ‡ Department of Chemistry, University of Alberta. Chem. Rev. 2009, 109, 4439–4486 4439

Applications of Orthogonal “Click” Chemistries in the Synthesis of Functional Soft Materials

Abstract: Department of Chemistry, Department of Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130, Department of Chemistry, Texas A&M University, College Station, Texas 77842, Cancer Center Karolinska, Department of Oncology-Pathology CCK, R8:03 Karolinska Hospital and Institute, SE-171 76 Stockholm, Sweden, and Department of Chemistry and Biochemistry, Department of Materials, and Materials Research Laboratory, University of California, Santa Barbara, California 93106

Organic Synthesis “On Water”

Abstract: Water is the lingua franca of life on our planet and is the solvent of choice for Nature to carry out her syntheses.1 In contrast, our methods of making complex organic molecules have taken us far away from the watery milieu of biosynthesis. Indeed, it is fair to say that most organic reactions commonly used both in academic laboratories and in industry fail in the presence of water or oxygen. As a direct consequence of our attempts to mimick Nature's way of making new chemical bonds, we learned to rely on highly reactive nucleophilic and electrophilic reagents to gain control of the chemical reactivity and to channel chemical reactions down a desired pathway. The requirement for the protection of all protic functional groups, such as alcohols and amines, is another corollary of our reliance on these energetic species. Nevertheless, chemical transformations in aqueous solvents are not new to organic chemists. On the contrary, they have attracted attention of scientists for many years: the first use of water for an organic reaction could be dated back to Wohler's synthesis of urea from ammonium cyanate.2 From a true organic synthesis perspective, the earliest example could be the synthesis of indigo by Baeyer and Drewsen in 1882 (Scheme 1).3 In their synthesis, a suspension of o-nitrobenzaldehyde 1 in aqueous acetone was treated with a solution of sodium hydroxide. The immediate formation of the characteristic blue color of indigo 2 ensued, and the product subsequently precipitated. Scheme 1 Water possesses many unique physical and chemical properties: large temperature window in which it remains in the liquid state, extensive hydrogen bonding, high heat capacity, large dielectric constant, and optimum oxygen solubility to maintain aquatic life forms. These distinctive properties are the consequence of the unique structure of water.4,5 The structure and properties of water have been studied by scientists representing almost all fields of knowledge, and new theoretical models continue to emerge.6,7 Water is also known to enhance the rates and to affect the selectivity of a wide variety of organic reactions.8,9 In spite of these potential advantages, water is still not commonly used as a sole solvent for organic synthesis, at least in part because most organic compounds do not dissolve in water to a significant extent, and solubility is generally considered a prerequisite for reactivity: “corpora non agunt nisi soluta” (substances do not react unless dissolved). Consequently, in the many examples of “aqueous reactions” organic co-solvents are employed in order to increase the solubility of organic reactants in water.9,10 Alternatively, hydrophilicity of the reactants is increased by the introduction of polar functional groups, again to make the resulting compound at least partially water soluble.11 However, these manipulations tend to diminish and even negate the advantages of low cost, simplicity of reaction conditions, ease of workup, and product isolation that water has over traditional solvents. Therefore, the currently burgeoning field of organic synthesis in aqueous media encompasses a large family of reactions. The solubility of reacting species and products can range from complete to partial to practically none, so that reaction mixtures can be both homogeneous and heterogeneous. The amount of water can also range widely, from substoichiometric quantities to a large volume in which the reactants are suspended or dissolved. Several terms have been used in the literature to describe reactions in aqueous millieu. In water, in the presence of water, and on water are commonly found in the recent publications and are often used interchangeably to describe reactions that proceed under very different conditions.12,13 There is also a growing number of examples micellar catalysis in the presence of non-ionic surfactants, such as Triton X-100 and PTS (a tocopherol-based amphiphile).14-18 In this review, we attempt to survey organic transformations that benefit from being performed on water under the conditions defined by Sharpless and co-workers: when insoluble reactant(s) are stirred in aqueous emulsions or suspensions without the addition of any organic co-solvents. In many cases, it is impossible to ascertain whether the reaction is occuring in or on water, but as long as the reaction mixture remains heterogeneous and the overall process appears to benefit from it (either in terms of increased reaction rate or enhanced selectivity), it qualifies. The ‘on water’ moniker reflects the defining attribute of these reactions: the lack of solubility of the reactant(s) in water. A considerable rate acceleration is often observed in reactions carried out under these conditions over those in organic solvents.19 Furthermore, in many cases a significant rate increase of on water reactions over reactions carried out neat indicates that rate acceleration is not merely a consequence of increased concentration of the reacting species. Naturally, the degree of on water acceleration varies between different reaction classes, and even when it is modest, there are other advantages to carrying out reactions in this manner. Firstly, water is an excellent heat sink due to its large heat capacity, making exothermic processes safer and more selective, especially when they are carried out on large scale. Secondly, reactions of water-insoluble substrates usually lead to the formation of water-insoluble products. In such cases, product isolation simply involves filtration of solid products (or phase separation in case of liquids). Finally, the growing list of examples wherein reactions performed on water are not only faster but also more selective (whether chemo-, regio-, or enantio-) underscores the significant potential for process intensification for reactions performed on water. Although claims of the ecological advantages and “greenness” of water are almost invariably found in the opening paragraphs of reports describing aqueous reactions, they should be taken with a grain of salt. The low cost, relative abundance, and inherent safety of water notwithstanding, the environmental impact of a process is determined by many factors, such as the efficiency of the reaction in terms of atom economy,20 the nature of solvents used in the reaction workup, the residual concentration of regulated organic compounds and metal catalysts remaining in the aqueous waste, and the costs of its clean up or disposal.21,22 The mere finding that a process performs as well in water as it does in an organic solvent tells us little about its potential environmental impact. The field of aqueous organic synthesis has been regularly and comprehensively reviewed.9,10,23-27 In addition, recent reviews focusing on microwave assisted organic synthesis in water,28 reactions in near-critical water,29 and biocatalysis in water30 have been published. Accordingly, these topics are not covered in the present review.

Helical polymers: synthesis, structures, and functions

Abstract: 2.2.1. Polyisocyanates 6117 2.2.2. Polysilanes 6118 2.2.3. Polyacetylenes 6120 2.3. Foldamer-Based Helical Polymers 6124 2.3.1. Click Polymerization 6126 2.3.2. Ring-Closing Reaction 6126 2.4. Other Types of Helical Polymers 6127 2.4.1. π-Conjugated Helical Polymers 6127 2.4.2. Metallosupramolecular Helical Polymers 6128 2.5. Induced Helical Polymers 6130 2.5.1. Induced Helical Polyacetylenes 6130 2.5.2. Other Induced Helical Polymers and Oligomers 6132

Ionic Liquids and Their Interaction with Cellulose

Abstract: Sustainability, industrial ecology, eco-efficiency, and green chemistry are directing the development of the next generation of materials, products, and processes. Biodegradable plastics and biocompatible composites generated from renewable biomass feedstock are regarded as promising materials that could replace synthetic polymers and reduce global dependence on fossil fuel sources.1 It is estimated that the world is currently consuming petroleum at a rate 100 000 times faster than nature can replace it.2 The growing global environmental awareness and societal concern, high rate of depletion of petroleum resources, concepts of sustainability, and new environmental regulations have triggered the search for new products and processes that are more compatible with the environment. The most abundant natural polymer in our environment is cellulose. It has an estimated annual biosphere production of 90 × 109 metric tons and, consequently, represents the most obvious renewable resource for producing biocomposites.3 Its highly ordered structure is responsible for its desirable mechanical properties but makes it a challenge to find suitable solvents for its dissolution.4 The first attempts to dissolve cellulose date back to the early 1920s.5 Several aqueous and nonaqueous cellulose solvents have been discovered since then, but all of these solvents suffer either from high environmental toxicity or from insufficient solvation power.6 In general, the traditional cellulose dissolution processes require relatively harsh conditions and the use of expensive and uncommon solvents, which usually cannot be recovered after the process.6-10 However, a new class of solvents was opened to the cellulose research community, when in 2002 Swatloski et al. reported the use of an ionic liquid as solvent for cellulose both for the regeneration of cellulose and for the chemical modification of the polysaccharide.7 In 1934, Graenacher had discovered a solvent system with the ability to dissolve cellulose, but this was thought to be of little practical value at the time.11,12 Ionic liquids are a group of salts that exist as liquids at relatively low temperatures (<100 °C). They have many attractive properties, including chemical and thermal stability, nonflammability, and immeasurably low vapor pressure.12 First discovered in 1914 by Walden, their huge potential in industry and research was only realized within the last few decades.13,14 This review aims to provide a summary of our current state of knowledge on the structural features of wood * To whom correspondence should be addressed. E-mail: ken.marsh@ canterbury.ac.nz. Tel.: +64 3364 2140. Fax: +64 3364 2063. † Department of Chemical and Process Engineering. ‡ Department of Mechanical Engineering. Andre Pinkert was born in Schwabach, Germany, in 1981. He studied Chemistry at the University of Erlangen-Nurnberg, Germany, and received his prediploma and diploma degrees in 2004 and 2008, respectively. During 2005, he joined the Marine Natural Products Group, lead by Murray H. Munro and John W. Blunt, at the University of Canterbury (UoC), New Zealand, working on the isolation and characterization of bioactive metabolites. In early 2006, he returned to Germany and resumed his studies at the University of Erlangen-Nurnberg, finishing his degree under the supervision of Rudi van Eldik. Associated with his studies, during 2007, he worked for AREVA NP on radio-nuclear chemistry and computer modeling. Since 2008, he is studying towards a Ph.D. degree at UoC under the supervision of Shusheng Pang, Ken Marsh, and Mark Staiger. His research focuses on biocomposites from natural fibers, processed via ionic liquids. Chem. Rev. 2009, 109, 6712–6728 6712

Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications.

Abstract: 3.2. Thienothiophenes 1216 3.2.1. Thieno[3,4-b]thiophene Analogues 1216 3.2.2. Thieno[3,2-b]thiophene Analogues 1217 3.2.3. Thieno[2,3-b]thiophene Analogues 1218 3.3. , ′-Bridged Bithiophenes 1219 3.3.1. Dithienothiophene (DTT) Analogues 1220 3.3.2. Dithieno[3,2-b:2′3′-d]thiophene-4,4-dioxides 1221 3.3.3. Dithienosilole (DTS) Analogues 1221 3.3.4. Cyclopentadithiophene (CPDT) Analogues 1221 3.3.5. Nitrogen and Phosphor Atom Bridged Bithiophenes 1222

Structural and functional analogues of the active sites of the [Fe]-, [NiFe]-, and [FeFe]-hydrogenases.

Abstract: This article sets out to review the chemistry relating to the synthesis of structural and functional analogues of the three classes of hydrogenases. This chemistry has grown explosively over the last 10 or so years since the first X-ray structures of [NiFe]- and [FeFe]-hydrogenase systems were published. There are now some 400 papers covering structural and functional aspects, with the majority of these associated with the di-iron system. As much emphasized in earlier papers

C-F bond activation in organic synthesis.

Abstract: Fluorine has received great attention in all fields of science. “Small atom with a big ego” was the title of the Symposium at the ACS meeting in San Francisco in 2000, where a number of the current scientific and industrial aspects of fluorine chemistry made possible by the small size and high electronegativity of the atom were discussed. This small atom has provided mankind with significant benefits in special products such as poly(tetrafluroethylene) (PTFE), freon, fluoro-liquid crystals, optical fiber, pharmaceutical and agrochemical compounds, and so on, all of which have their own unique properties that are otherwise difficult to obtain.1 For instance, at present, up to 30% of agrochemicals and 10% of pharmaceuticals currently used contain fluorine atoms. Therefore, organic fluorine compounds have received a great deal of interest and attention from the scientists involved in diverse fields of science and technology. Now, not only C-F bond formation but also selective C-F bond activation have become current subjects of active investigation from the viewpoint of effective synthesis of fluoroorganic compounds. The former is highlighted by designing a sophisticated fluorinating reagent for regioand stereocontrolled fluorination and developing versatile multifunctional and easily prepared building blocks. C-F bond formation has been treated extensively in several reviews2 and books.3 The latter is a subject that has been less explored but would be promising for selective defluorination of aliphatic fluorides, cross-coupling with aryl fluorides, and * To whom correspondence should be addressed. Phone: 81-78-803-5799. Fax: 81-78-803-5799. E-mail: amii@kobe-u.ac.jp and uneyamak@cc.okayamau.ac.jp. † Kobe University. ‡ Okayama University. Chem. Rev. 2009, 109, 2119–2183 2119

Transition metal-catalyzed living radical polymerization : toward perfection in catalysis and precision polymer synthesis

Abstract: 2.1.6. Tacticity and Sequence: Advanced Control 4967 2.2. Transition Metal Catalysts 4967 2.2.1. Overviews of Catalysts 4967 2.2.2. Ruthenium 4967 2.2.3. Copper 4971 2.2.4. Iron 4971 2.2.5. Nickel 4975 2.2.6. Molybdenum 4975 2.2.7. Manganese 4976 2.2.8. Osmium 4976 2.2.9. Cobalt 4976 2.2.10. Other Metals 4976 2.3. Cocatalysts (Additives) 4977 2.3.1. Overview of Cocatalysts 4977 2.3.2. Reducing Agents 4977 2.3.3. Free Radical Initiators 4977 2.3.4. Metal Alkoxides 4977 2.3.5. Amines 4978 2.3.6. Halogen Source 4978 2.4. Initiators 4978 2.4.1. Overview of Initiators: Scope and Design 4978 2.4.2. Alkyl Halides 4978 2.4.3. Arenesulfonyl Halides 4979 2.4.4. N-Chloro Compounds 4979 2.4.5. Halogen-Free Initiators 4979 2.5. Solvents 4980 2.5.1. Overview of Solvents 4980 2.5.2. Catalyst Solubility and Coordination of Solvent 4981 2.5.3. Environmentally Friendly Solvents 4981 2.5.4. Water 4981 2.5.5. Catalytic Solvents: Catalyst Disproportionation 4981

Impact of natural products on developing new anti-cancer agents

Abstract: 3.3.1. Potential of the “Metagenome” 3016 3.3.2. Cryptic Clusters in Bacteria and Fungi 3016 3.3.3. Cyanophytes 3017 3.3.4. Marine Microbes (Non-Cyanophytes) 3018 3.3.5. Extremophiles 3018 3.3.6. Microbial Symbionts 3019 3.3.7. Plant Endophytes 3020 3.3.8. Combinatorial Biosynthesis 3020 4. Development of Drugs from Natural Products 3020 4.1. Synthesis Based on Natural Products 3021 4.1.1. Derivatization and Semisynthesis 3021 4.1.2. Total Synthesis 3021 4.1.3. Diverted Total Synthesis 3021 4.2. Natural Product-Inspired Combinatorial Synthesis 3022

Mechanically-induced chemical changes in polymeric materials

Abstract: Engineering applications of synthetic polymers are widespread due to their availability, processability, low density, and diversity of mechanical properties (Figure 1a). Despite their ubiquitous nature, modern polymers are evolving into multifunctional systems with highly sophisticated behavior. These emergent functions are commonly described as “smart” characteristics whereby “intelligence” is rooted in a specific response elicited from a particular stimulus. Materials that exhibit stimuli-responsive functions thus achieve a desired output (O, the response) upon being subjected to a specific input (I, the stimulus). Given that mechanical loading is inevitable, coupled with the wide range of mechanical properties for synthetic polymers, it is not surprising that mechanoresponsive polymers are an especially attractive class of smart materials. To design materials with stimuli-responsive functions, it is helpful to consider the I-O relationship as an energy transduction process. Achieving the desired I-O linkage thus becomes a problem in finding how to transform energy from the stimulus into energy that executes the desired response. The underlying mechanism that forms this I-O coupling need not be a direct, one-step transduction event; rather, the overall process may proceed through a sequence of energy transduction steps. In this regard, the network of energy transduction pathways is a useful roadmap for designing stimuli-responsive materials (Figure 1b). It is the purpose of this review to broadly survey the mechanical to chemical * To whom correspondence should be addressed. Phone: 217-244-4024. Fax: 217-244-8024. E-mail: jsmoore@illinois.edu. † Department of Chemistry and Beckman Institute. ‡ Department of Materials Science and Engineering and Beckman Institute. § Department of Aerospace Engineering and Beckman Institute. Chem. Rev. XXXX, xxx, 000–000 A

Dendron-Mediated Self-Assembly, Disassembly, and Self-Organization of Complex Systems

Abstract: Dendron-mediated self-assembly, disassembly, and self-organization of complex systems have been investigated. The most ideal building blocks would need to display shape persistence in solution and in the solid state, since only this feature provides access to the use of complementary methods of structural analysis. Most supramolecular dendrimers are chiral even when they are constructed from nonchiral building blocks and are equipped with mechanisms that amplify chirality. This poses additional challenges associated with the understanding of the structural origin of chirality in different supramolecular structures through combinations of structural analysis methods. While many supramolecular structures assembled from dendrimers and dendrons resemble some of the related morphologies generated from block-copolymers, they are much more complex and are not determined by the volume ratio between the dissimilar parts of the molecule.

Acetylenic polymers: syntheses, structures, and functions.

Abstract: Department of Chemistry, William Mong Institute of Nano Science and Technology, Bioengineering Graduate Program, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China, and Department of Polymer Science and Engineering, Key Laboratory of Macromolecular Synthesis and Functionalization of the Ministry of Education, Institute of Biomedical Macromolecules, Zhejiang University, Hangzhou 310027, China

Hyperbranched and highly branched polymer architectures--synthetic strategies and major characterization aspects.

Abstract: “Life is branched” was the motto of a special issue of Macromolecular Chemistry and Physics1 on “Branched Polymers”, indicating that branching is of similar importance in the world of synthetic macromolecules as it is in nature. The significance of branched macromolecules has evolved over the last 30 years from just being considered as a side reaction in polymerization or as a precursor step in the formation of networks. Important to this change in perception of branching was the concept of “polymer architectures”, which formed on new starand graft-branched structures in the 1980s and then in the early 1990s on dendrimers and dendritic polymers. Today, clearly, controlled branching is considered to be a major aspect in the design of macromolecules and functional material. Hyperbranched (hb) polymers are a special type of dendritic polymers and have as a common feature a very high branching density with the potential of branching in each repeating unit. They are usually prepared in a one-pot synthesis, which limits the control on molar mass and branching accuracy and leads to “heterogeneous” products with a distribution in molar mass and branching. This distinguishes hyperbranched polymers from perfectly branched and monodisperse dendrimers. In the last 20 years, both classes of dendritic polymers, dendrimers as well as hb polymers, have attracted major attention because of their interesting properties resulting from the branched architecture as well as the high number of functional groups.2 The challenging synthesis of the dendrimers attracted especially scientists with a strong organic chemistry background and led to beautifully designed macromolecules, which allowed a deeper insight into the effect of branching and functionality. Dendrimers have been considered as perfect “nano-objects” where one can control perfectly size and functionality, which is of high interest in nanotechnology and biomedicine. hb polymers, however, were considered from the beginning as products suitable for larger-scale application in typical polymer fields like coatings and resins, where a perfect structure is sacrificed for an easy and affordable synthetic route. Thus, the first structures that were reported paralleled the chemistry used for linear polymers like typical polycondensation for polyester synthesis. More recently, unconventional synthetic methods have been adopted also for hb polymers and related structures. Presently, a vast variety of highly branched structures have been realized and studied regarding their properties and potential application fields. Excellent reviews appeared covering synthesis strategies, properties, and applications, like the very recent tutorial by Carlmark et al.,3 the comprehensive book on hyperbranched polymers covering extensively synthesis and application * E-mail: voit@ipfdd.de; lederer@ipfdd.de. Chem. Rev. 2009, 109, 5924–5973 5924

Nitrogen cycle electrocatalysis.

Abstract: After carbon, hydrogen, and oxygen, nitrogen is the next most abundant element in the human body. Inorganic and organic compounds of nitrogen feature prominently in many biological and environmental, as well as industrial, processes. In nature, the inorganic compounds of nitrogen are controlled by a reaction cycle called the nitrogen cycle (Figure 1).1 The denitrification pathway in this cycle, that is, the conversion of nitrate to dinitrogen, is employed by certain bacteria to produce ATP anaerobically and gain energy for cell growth. All organisms use ammonia as one of the starting building blocks for the synthesis of amino acids, nucleotides, and many other important biological compounds. Nitric oxide is * Corresponding author. E-mail: m.koper@chem.leidenuniv.nl. † Present address: Energy research Centre of The Netherlands (ECN), P.O. Box 1, 1755 ZG Petten, The Netherlands. ‡ Present address: Research, Development & Innovation, AkzoNobel Chemicals bv, Velperweg 76, P.O. Box 9300, 6800 SB Arnhem, The Netherlands. Chem. Rev. 2009, 109, 2209–2244 2209

Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

Abstract: N atom, thus providing carbenes derived from pyrazolium, isothiazolium, and even quinolinium salts that contain a stabilizing heteroatom in a remote position (G-J in Figure 1). Recently, carbenes such as K, which are comprised of only one heteroatom and lack delocalization through the heterocycle, have been discovered as versatile ligands, thus constituting another important class of carbenes with low heteroatom stabilization. Both the synthesis of the organometallic complexes of these ligands as well as the (catalytic) properties of the coordinated metal centers generally show distinct differences, compared to the more classical NHC complexes, such as C2-metallated imidazolylidenes. This review intends to describe such differences and highlights the chemical peculiarities of these types of N-heterocyclic carbene complexes. It introduces, in a qualitative manner, the synthetic routes that have been established for the preparation of such complexes, covering the literature from the very beginning of activities in this area up to 2008. While specialized reviews on some aspects of the present topic have recently appeared,7 a comprehensive overview of the subject has not been available thus far. Rather than just being descriptive, the present account is mainly directed toward the impact of these still unusual metal-carbene bonding modes on the electronic properties and on the new catalytic applications that have been realized by employing such new carbene complexes. As a consequence of our focus on complexes with less-stabilized heterocyclic ligands, systems comprising acyclic carbenes have not been included, and the interested reader is, instead, referred to the pioneering and

Mitsunobu and Related Reactions: Advances and Applications

Abstract: 10. Patented Literature 2616 10.1. Esterification 2616 10.2. Ether Formation 2619 10.2.1. Etherification without Cyclization 2619 10.2.2. Etherification with Cyclization 2624 10.3. N-Alkylation 2625 10.4. Other Reactions 2627 11. Summary and Outlook 2628 12. Note Added in Proof 2628 13. Abbreviations Used in This Review 2629 14. Acknowledgments 2629 15. Supporting Information Available 2630 16. References 2630

Coinage Metal−N-Heterocyclic Carbene Complexes

Abstract: 2.3.5. Multi-NHCs Linked by Spacers 3568 2.4. The Ag2O Route 3570 2.4.1. Feasibility 3570 2.4.2. Complications 3571 2.4.3. Theoretical Consideration 3572 2.5. Applications 3572 2.5.1. Ag(I)-NHCs in NHC Transfer 3572 2.5.2. Ag(I)-NHCs in Catalysis 3572 2.5.3. Ag(I)-NHCs in Medicine 3572 2.5.4. Ag(I)-NHCs in Nanomaterials 3573 3. Au(I)and Au(III)-NHCs 3573 3.1. Historical Background 3573 3.2. General Synthetic Methods 3573 3.3. Formation of Au(I)and Au(III)-NHCs 3574 3.3.1. Neutral [Au(NHC)L] 3574 3.3.2. Ionic [Au(NHC)L][Anion] 3576 3.3.3. Multinuclear Au(I)-NHCs 3578 3.3.4. Other Classes of Au(I)-NHCs 3578 3.3.5. Au(III)-NHC Complexes 3579 3.4. Applications 3579 3.4.1. Au(I)and Au(III)-NHCs in Catalysis 3579 3.4.2. Au(I)-NHCs in Medicine 3580 4. Cu(I)and Cu(II)-NHCs 3581 4.1. Historical Background 3581 4.2. General Synthetic Methods 3582 4.3. Formation of Cu(I)and Cu(II)-NHCs 3583 4.3.1. Complexes Containing the Cu(NHC)2 Core 3583 4.3.2. [Cu(NHC)(Halide)] 3583 4.3.3. [Cu(NHC)(Ligand)] 3584 4.3.4. Multinuclear Cu(I)and Cu(II)-NHCs 3589 4.4. Catalysis 3591 4.4.1. Past Events 3591 4.4.2. Recent Advancements 3591 5. Photoluminescence 3592 6. Conclusions 3594 7. Abbreviations 3594 8. Acknowledgments 3595 9. References 3595