Although homogeneous gold catalysis was known previously, an exponential growth was only induced 12 years ago. The key findings which induce that rise of the field are discussed. This includes early reactions of allenes and furanynes and intermediates of these conversions as well as hydroarylation reactions. Other substrate types addressed are alkynyl epoxides and N-propargyl carboxamides. Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.

Gold-Catalyzed Organic Reactions

/pdf/lanthanide-single-molecule-magnets-efv9mucvem.pdf

Lanthanide single-molecule magnets.

The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization. The quite remarkable correlation of their catalytic behavior with the available structural data, coordination chemistry, and organometallic reactivity patterns, including relativistic effects, allows the underlying principles of catalytic carbophilic activation by π acids to be formulated. The spectrum of reactivity extends beyond their utility as catalytic and benign alternatives to conventional stoichiometric π acids. The resulting reactivity profile allows this entire field of catalysis to be rationalized, and brings together the apparently disparate electrophilic metal carbene and nonclassical carbocation explanations. The advances in coupling, cycloisomerization, and structural reorganization—from the design of new transformations to the improvement to known reactions—are highlighted in this Review. The application of platinum- and gold-catalyzed transformations in natural product synthesis is also discussed.

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

1.1. Context and Meta-Review
Despite the ubiquity of metallic gold (Au) in popular culture, its deployment in homogeneous catalysis has only recently undergone widespread investigation. In the past decade, and especially since 2004, great progress has been made in developing efficient and selective Au-catalyzed transformations, as evidenced by the prodigious number of reviews available on various aspects of this growing field. Hashmi has written a series of comprehensive reviews outlining the progression of Au-catalyzed reaction development,1 and a number of more focused reviews provide further insight into particular aspects of Au catalysis. A brief meta-review of the available range of perspectives published on Au catalysis helps to put this Chemical Reviews article in context.

The vast majority of reactions developed with homogeneous Au catalysts have exploited the propensity of Au to activate carbon-carbon π-bonds as electrophiles. Gold has come to be regarded as an exceedingly mild, relatively carbophilic Lewis acid, and the broad array of newly developed reactions proceeding by activation of unsaturated carbon-carbon bonds has been expertly reviewed.2

Further reviews and highlights on Au catalysis focus on particular classes of synthetic reactions. An excellent comprehensive review of Au-catalyzed enyne cycloisomerizations is available.3 Even more focused highlights on hydroarylation of alkynes,4 hydroamination of C-C multiple bonds,5 and reactions of oxo-alkynes6 and propargylic esters7 provide valuable perspectives on progress and future directions in the development of homogeneous Au catalysis.

Most of the reviews on Au catalysis emphasize broad or specific advances in synthetic utility. Recently, we have invoked relativistic effects to provide a framework for understanding the observed reactivity of Au catalysts, in order to complement empirical advancements.8 In this Chemical Reviews article, we attempt to enumerate the ways in which selectivity can be controlled in homogeneous Au catalysis. It is our hope that lessons to guide catalyst selection and the design of new catalysts may be distilled from a thorough evaluation of ligand, counterion, and oxidation state effects as they influence chemo-, regio-, and stereoselectivity in homogeneous Au catalysis.

http://www.cchem.berkeley.edu/toste/publications/cr068430g.pdf

Ligand effects in homogeneous Au catalysis.

In recent years, tremendous research effort has been aimed at increasing the energy density of supercapacitors without sacrificing high power capability so that they reach the levels achieved in batteries and at lowering fabrication costs For this purpose, two important problems have to be solved: first, it is critical to develop ways to design high performance electrode materials for supercapacitors; second, it is necessary to achieve controllably assembled supercapacitor types (such as symmetric capacitors including double-layer and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors) The explosive growth of research in this field makes this review timely Recent progress in the research and development of high performance electrode materials and high-energy supercapacitors is summarized Several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters are reviewed, and challenges and perspectives in this exciting field are also discussed This provides fundamental insight into supercapacitors and offers an important guideline for future design of advanced next-generation supercapacitors for industrial and consumer applications

Recent Advances in Design and Fabrication of Electrochemical Supercapacitors with High Energy Densities

It is a challenge to synthesize materials that possess the properties of biological muscles-strong, elastic and capable of self-healing. Herein we report a network of poly(dimethylsiloxane) polymer chains crosslinked by coordination complexes that combines high stretchability, high dielectric strength, autonomous self-healing and mechanical actuation. The healing process can take place at a temperature as low as -20 °C and is not significantly affected by surface ageing and moisture. The crosslinking complexes used consist of 2,6-pyridinedicarboxamide ligands that coordinate to Fe(III) centres through three different interactions: a strong pyridyl-iron one, and two weaker carboxamido-iron ones through both the nitrogen and oxygen atoms of the carboxamide groups. As a result, the iron-ligand bonds can readily break and re-form while the iron centres still remain attached to the ligands through the stronger interaction with the pyridyl ring, which enables reversible unfolding and refolding of the chains. We hypothesize that this behaviour supports the high stretchability and self-healing capability of the material.

A highly stretchable autonomous self-healing elastomer

A stiff and healable polymer is obtained by using the dynamic-covalent boroxine bond to crosslink PDMS chain into 3D networks. The as-prepared polymer is very strong and stiff, and can bear a load of more than 450 times its weight. When damaged, it can be completely healed upon heating after wetting.

A Stiff and Healable Polymer Based on Dynamic-Covalent Boroxine Bonds

Self-healing ability is an important survival feature in nature, with which living beings can spontaneously repair damage when wounded. Inspired by nature, people have designed and synthesized many self-healing materials by encapsulating healing agents or incorporating reversible covalent bonds or noncovalent interactions into a polymer matrix. Among the noncovalent interactions, the coordination bond is demonstrated to be effective for constructing highly efficient self-healing polymers. Moreover, with the presence of functional metal ions or ligands and dynamic metal-ligand bonds, self-healing polymers can show various functions such as dielectrics, luminescence, magnetism, catalysis, stimuli-responsiveness, and shape-memory behavior. Herein, the recent developments and achievements made in the field of self-healing polymers based on coordination bonds are presented. The advantages of coordination bonds in constructing self-healing polymers are highlighted, the various metal-ligand bonds being utilized in self-healing polymers are summarized, and examples of functional self-healing polymers originating from metal-ligand interactions are given. Finally, a perspective is included addressing the promises and challenges for the future development of self-healing polymers based on coordination bonds.

Self-Healing Polymers Based on Coordination Bonds.

Adopting self-healing, robust, and stretchable materials is a promising method to enable next-generation wearable electronic devices, touch screens, and soft robotics. Both elasticity and self-healing are important qualities for substrate materials as they comprise the majority of device components. However, most autonomous self-healing materials reported to date have poor elastic properties, i.e., they possess only modest mechanical strength and recoverability. Here, a substrate material designed is reported based on a combination of dynamic metal-coordinated bonds (β-diketone-europium interaction) and hydrogen bonds together in a multiphase separated network. Importantly, this material is able to undergo self-healing and exhibits excellent elasticity. The polymer network forms a microphase-separated structure and exhibits a high stress at break (≈1.8 MPa) and high fracture strain (≈900%). Additionally, it is observed that the substrate can achieve up to 98% self-healing efficiency after 48 h at 25 °C, without the need of any external stimuli. A stretchable and self-healable dielectric layer is fabricated with a dual-dynamic bonding polymer system and self-healable conductive layers are created using polymer as a matrix for a silver composite. These materials are employed to prepare capacitive sensors to demonstrate a stretchable and self-healable touch pad.

Cheng-Hui Li

Papers

A highly stretchable autonomous self-healing elastomer

A Stiff and Healable Polymer Based on Dynamic-Covalent Boroxine Bonds

Self-Healing Polymers Based on Coordination Bonds.

An Elastic Autonomous Self-Healing Capacitive Sensor Based on a Dynamic Dual Crosslinked Chemical System

Single-ion magnets based on mononuclear lanthanide complexes with chiral Schiff base ligands [Ln(FTA)3L] (Ln = Sm, Eu, Gd, Tb and Dy).