The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck-Type-lautens.pdf

Aryl-aryl bond formation by transition-metal-catalyzed direct arylation.

介绍了Kirk—Othmer Encyclopedia of Chemical Technology（化工技术百科全书）（第五版）电子图书网络版数据库，并对该数据库使用方法和检索途径作出了说明，且结合实例简单地介绍了该数据库的检索方法。

Kirk-Othmer Encyclopedia of Chemical Technology数据库介绍及实例

Polyoxometalates represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form structures that can bridge several length scales. The new building block principles that have been discovered are beginning to allow the design of complex clusters with desired properties and structures and several structural types and novel physical properties are examined. In this critical review the synthetic and design approaches to the many polyoxometalate cluster types are presented encompassing all the sub-types of polyoxometalates including, isopolyoxometalates, heteropolyoxometalates, and reduced molybdenum blue systems. As well as the fundamental structure and bonding aspects, the final section is devoted to discussing these clusters in the context of contemporary and emerging interdisciplinary interests from areas as diverse as anti-viral agents, biological ion transport models, and materials science.

Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices

Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale Herein we present the very latest developments from synthesis to structure and function of POMs We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features We propose and present a "periodic table of polyoxometalate building blocks" We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

The applications of copper (Cu) and Cu-based nanoparticles, which are based on the earth-abundant and inexpensive copper metal, have generated a great deal of interest in recent years, especially in the field of catalysis. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. In addition, the design and development of novel support and/or multimetallic systems (e.g., alloys, etc.) has also made significant contributions to the field. In this comprehensive review, we report different synthetic approaches to Cu and Cu-based nanoparticles (metallic copper, copper oxides, and hybrid copper nanostructures) and copper nanoparticles immobilized into or supported on various support materials (SiO2, magnetic support materials, etc.), along with their applications i...

http://pubs.acs.org/doi/pdfplus/10.1021/acs.chemrev.5b00482

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis.

In the presence of Rh(2)(OAc)(4) (OAc = acetate) and TBA(2)WO(4) (TBA = tetra-n-butylammonium), the N-silylation of indole derivatives with hydrosilanes efficiently proceeded to give the corresponding N-silylated indoles in high yields. Pyrrole and carbazole were also N-silylated with the combined catalysts.

Rhodium Acetate/Base-Catalyzed N-Silylation of Indole Derivatives with Hydrosilanes.

Present energy issues have increasingly stimulated the demand for the development of clean and sustainable energy platforms which can achieve net zero carbon emissions. Renewable energy resources are quite promising candidates for the construction of sustainable decarbonized society. One of examples of harnessing renewable energy-derived electricity is the electrolysis of earth-abundant water into hydrogen, which is a prominent carbon-free chemical fuel with a high weight energy density. Compared with polymer electrolyte water electrolysis in acidic environment, electrochemical alkaline water splitting can employ inexpensive nonprecious metals as electrocatalysts, which can make this technology a large-scale and cost-effective process. However, the anodic oxygen evolution reaction (OER) in the water splitting has a large overpotential, and it is a great bottleneck for widespread use. Thus, highly active and inexpensive electrocatalysts for OER are desired to overcome this concern.
 Iron (Fe) is a very earth-abundant element that is a quite cheap and non-toxic metal, and thus it is a potential candidate as electrocatalyst for OER. Previous studies have reported several multimetal oxides with Fe and other metallic elements, such as perovskite and brownmillerite types, which have attracted great attentions due to their facile synthesis and easily tunable OER activities by element substitution and doping. However, most of these studies focused on the choice of elements. Contrarily, the effects of crystal structures on OER activity have not yet been sufficiently interpreted, and it can be a crucial aspect to understand the OER electrocatalysis on Fe-based oxides and for the rational design of outstanding OER catalysts.
 In this study, we aim to comprehensively understand the effects of crystal structures on electrocatalytic OER activities on Fe-based oxides. To obtain versatile insights into OER electrocatalysis, we collected OER performances of Fe-based simple and bimetal oxides from our experiments and literature, and their structural characteristics were obtained from databases for inorganic compounds. Thus, we found that OER efficiencies on the Fe-based oxides were correlated with Fe–O bond lengths in their crystals; i.e., a shorter Fe–O bond length led to a higher OER activity.[1] We then exploited databases to mine potential candidates based on the structure–activity relationship and selected unreported Fe-based bimetal and trimetal oxides with various structures, which can dramatically accelerate our catalyst research. We synthesized these Fe-based multimetal oxides and evaluated their OER activity in alkaline media; remarkably, the OER efficiency on the unreported Fe-based multimetal oxides also exhibited excellent correlation with Fe–O bond lengths, as plotted in Figure 1. It is notable that the trend in the Fe–O bond length and OER activity is applicable to a wide variety of Fe-based simple, bimetal, and trimetal oxides regardless of chemical compositions, crystal categories, and Fe valence states. Furthermore, machine learning analysis proved that Fe–O bond length is the most dominant structural descriptor for OER efficiency compared with other structural parameters.[2] However, it is required to overcome the abovementioned catalytic trend because theoretical Fe–O bond length in Fe-based oxides is limited, and superior OER catalysts cannot be achieved according to this design guideline. Hence, we attempted to switch the OER electrocatalytic mechanism on a Fe-based oxide by the arrangement of crystal structure because different mechanisms should be involved in different descriptors; i.e., the mechanism switch could surpass the abovementioned catalytic trend. Thus, we found post-spinel CaFe2O4 that comprises a large amount of edge-shared FeO6 connectivity in its crystal. DFT calculations unveiled that the structural characteristics induced an unprecedented OER mechanism, multi-iron-site mechanism, where OER process goes through a reaction intermediate with an O–O bridge on multiple Fe sites as depicted in upper side in Figure 1. Consequently, CaFe2O4 exhibited prominent OER activity despite long Fe–O bond length in its crystal.[3] These findings provide a novel insight into the OER electrocatalysis on Fe-based oxides and contribute to the innovation of electrochemical hydrogen production.
 The part of this paper is based on results obtained from a project, JPNP14021, commissioned by the New Energy and Industrial Technology Development Organization (NEDO). Authors acknowledge the PRESTO program (No. JPMJPR15S3) of the JST. The part of DFT calculations was carried out on the supercomputers at NIMS, Hokkaido Univ., Kyushu Univ., and the HPCI systems (project codes: hp180115, hp200131). The part of this work was supported by JSPS KAKENHI Grant Number 20H00314 and 20K15087.
 
 References
 
 [1] Y. Sugawara, K. Kamata, E. Hayashi, M. Itoh, Y. Hamasaki, T. Yamaguchi ChemElectroChem, 2021, 8, 4466.
 [2] Y. Sugawara. S. Ueno, K. Kamata, T. Yamaguchi, ChemElectroChem, 2022, 9, in press.
 [3] Y. Sugawara, K. Kamata, A. Ishikawa, Y. Tateyama, T Yamaguchi, ACS Appl. Energy Mater., 2021, 4, 3057.
 
 
 
 
 
 Figure 1


Crystal Structure-Controlled Electrocatalysis on Iron-Based Oxides Toward Oxygen Evolution in Alkaline Media: Trend and Mechanism

The use of an organic-solvent-soluble phosphate as the catalyst allows the challenging N-alkylation of indoles with α,β-unsaturated esters, amides, and nitriles.

Selective N-Alkylation of Indoles with α,β-Unsaturated Compounds Catalyzed by a Monomeric Phosphate.

A heterogenous catalyst comprising of tungsten and zinc oxides (3.5 wt% W and 0.8 wt% Zn) on SnO2 support is found to efficiently promote the epoxidation of alkenes and the oxidation of amines, silanes, and sulfide by hydrogen peroxide.

Efficient Heterogeneous Epoxidation of Alkenes by a Supported Tungsten Oxide Catalyst.

(Pr4N)[WOCl(O2)2(H2O)] is synthesized by addition of (Pr4N)Cl to an aqueous solution of H2WO4, H2O2, and HCl (273 K, 10 min, 73% yield).

Keigo Kamata

Papers

Rhodium Acetate/Base-Catalyzed N-Silylation of Indole Derivatives with Hydrosilanes.

Crystal Structure-Controlled Electrocatalysis on Iron-Based Oxides Toward Oxygen Evolution in Alkaline Media: Trend and Mechanism

Selective N-Alkylation of Indoles with α,β-Unsaturated Compounds Catalyzed by a Monomeric Phosphate.

Efficient Heterogeneous Epoxidation of Alkenes by a Supported Tungsten Oxide Catalyst.

Novel All-inorganic Mononuclear Chloro Oxo Diperoxotungstate.