Photoredox Catalysis Using Heterogenized Iridium Complexes**

Heterogenized photoredox catalysts provide a path for sustainable chemical synthesis using highly tunable, reusable constructs. Here, heterogenized iridium complexes as photoredox catalysts were assembled via covalent attachment to metal oxide surfaces (ITO, ZrO₂, Al₂O₃) in thin film or nanopowder constructs. The goal was to understand which materials provided the most promising constructs for catalysis. To do this, reductive dehalogenation of bromoacetophenone to acetophenone was studied as a test reaction for system optimization. All catalyst constructs produced acetophenone with high conversions and yields with the fastest reactions complete in fifteen minutes using Al₂O₃ supports. The nanopowder catalysts resulted in faster and more efficient catalysis, while the thin film catalysts were more robust and easily reused. Importantly, the thin film constructs show promise for future photoelectrochemical and electrochemical photoredox setups. Finally, all catalysts were reusable 2–3 times, performing at least 1000 turnovers (Al₂O₃), demonstrating that heterogenized catalysts are a sustainable catalyst alternative.     

粘土层间金属络合物催化剂及其分子识别催化作用

粘土的可膨胀的二维空间有助于将催化活性的金属络合物阳离子交换法和配位体交换法插入到粘土层间,因而易于制得粘土层间金属络合物催化剂,这是均相催化剂多相化的一种好方法,粘土层间金属络合物催化剂具有分子识别催化作用,择形选择性,立体选择性,区域选择性,本文论述了多种多相化催化剂上的对不对称加氢反尖,区域选择加氢反应,区域选择羰基化反应和空间选择芳基化反应,粘土层间金属络合物催化剂有高的活性和选择性,它可以与匀相金属络合物催化剂相媲美。     

Study of Palladium Complexes with Chitosan and Its Derivatives as Potential Catalysts for Terminal Olefin Oxidation

FTIR spectroscopy and XPS are used to study palladium complexes with various forms of chitosan: initial and modified by glutaric aldehyde. IR bands are identified that are related to the Pd–N and Pd–O bonds. A difference between the spectra of complexes obtained by the methods of adsorption and coprecipitation of chitosanium hydrochloride with the tetrachloropalladate ion is found. It is shown that the systems studied can be used as catalysts for terminal olefin oxidation by oxygen in the presence of H₂O₂. In the course of the reaction, the complexes undergo redox transformations without breaking the structure of the complex or metal transfer to the reaction mixture. The use of heterogenized Pd(II) complexes as catalysts in terminal olefin oxidation leads to the formation of oxidation and isomerization products, similarly to the case of homogeneous oxidation.     

Ordered Mesoporous Silica as Supports in the Heterogeneous Asymmetric Catalysis

Enantioselective synthesis of organic compounds has been studied by homogeneous catalysts for several years. However, these catalysts have yet to make a significant impact on industrial scales for fine chemical synthesis. A primary reason is the designing of a homogeneous asymmetric catalyst, which requires relatively bulky ligands and catalyst recovery and recycling often causes problems. One of the convincing ways to overcome this problem is to immobilise the asymmetric catalyst onto a solid support and the resulting heterogeneous asymmetric catalyst system can, in principle, be readily re-used. A large number of supports such as inorganic oxides including zeolites, alumina, zirconia, silica and organic polymers have been employed as supports in heterogeneous asymmetric catalysis. Therefore, in this review article we have summarized the work done by us in our laboratory on the immobilization of chiral transition metal complexes such as Ru, Ir, Mn and Ti onto ordered mesoporous silica and its asymmetric catalysis. All these immobilized catalysts were well characterized by different physicochemical techniques to confirm the structural retention of the support as well as the active metal complex after immobilization. This report includes our asymmetric catalytic investigations in enantioselective reactions such as hydrogenation of ketones, olefins, oxidation of sulfides and oxidative kinetic resolution of alcohols and sulfoxides through immobilized heterogeneous catalyst systems.     

Addition of carbon tetrachloride to olefins in the presence of copper complexes with polyfunctional ligands chemically immobilized on the surface of silica

Homogeneous and heterogeneous catalysts containing copper complexes with amino alcohols and hydroxy amino acids were synthesized. Heterogenized systems were immobilized on the surface of silica by covalent bonding of the hydroxyl groups of ligands to the silanol groups of silica. The resulting complexes were active in the reactions of CCl₄ addition to multiple bonds of olefins. In the case of 1-octene, the activity of heterogeneous catalysts was an extremal function of metal concentration on the surface, whereas a symbatic relationship was observed for a chlorinated olefin (allyl chloride). The above effects were explained by the participation of different copper complexes, in particular, of different nuclearity, in reactions with different olefins.Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 80–84.Original Russian Text Copyright © 2005 by Smirnov, Tarkhanova, Kokorin, Gantman, Tsvetkov     

Back Cover: Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions (Angew. Chem. Int. Ed. 21/2023)

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.     

Structure and catalytic activity of metallocomplexes immobilized on carriers

Mono-, bi-, and trinuclear Ru complexes with various ligands immobilized on the surface of silica gels modified with -aminopropyl, formamide, sulfide, cyano, or mercapto groups, catalyze hydrodehalogenation ofp-bromotoluene by the transfer of hydrogen from NaBH4 in 2-propanol both in an Ar atmosphere and in air. The structures of the heterogenized metallocomplex catalysts prepared (the nature of the ligand environment, the oxidation number of the central atom) were studied by IR and XP spectroscopy. The immobilized binuclear Ru^II,III tetraacetate, which retains the structure of the original complex, exhibits higher catalytic activity in the hydrogenolysis ofp-bromotoluene than heterogenized mononuclear systems.For Part 5, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 70–74, January, 1995.     

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Intermediates for many catalysis reactions reported in the literature are metal‐alkyl and metal‐alkenyl, including metallacycloalkane species. Synthesis and reactions of metal‐alkyl, alkenyl and metallacyle complexes have shown a great deal of development during the past few decades. This review summarizes the significant contributions reported on metal‐alkenyl compounds, specifically those containing at least a carbon chain with pendant alkene group [M―CH₂CH₂CH?CH₂]. Although metal‐alkenyl complexes are stable with strong chelating diphosphines and with a decrease in the ligand donor strength, the complexes can decompose without any ambiguity. For example, platinum‐dialkenyl complexes react readily via β‐hydrogen elimination and reductive elimination promoted by the nature of the ligand, solvent and length of carbon chains. These complexes can also undergo intramolecular irreversible isomerization and this leads to the selective catalytic isomerization of 1‐alkenes to 2‐alkenes in the presence of platinum‐dialkenyl complexes as catalysts. Perhaps the most striking manifestations of flexibility are the facile and complete intramolecular and intermolecular alkene metathesis to yield the corresponding metallacycloalkenes in the presence of Grubbs’ catalysts. The diverse chemical reactivity of these complexes demonstrates both the scope and complexity of metal‐alkenyl chemistry depending on the nature of ligand and metal. Copyright © 2014 John Wiley & Sons, Ltd.     

Nickel and palladium <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene complexes. Synthesis and application in cross-coupling reactions

N-Heterocyclic carbenes (NHCs) are widely used as ligands in catalysis by transition metal complexes. The catalytic activity of transition metal NHC complexes is much higher than that of the transition metal complexes bearing the phosphine and nitrogen-containing ligands. They show excellent catalytic performance in different transformations of the organic compounds, especially in the carbon—carbon and carbon—element bond forming reactions. Palladium NHC complexes are very efficient catalysts for the cross-coupling reactions. On the other hand, nickel is less expensive and regarded as a promising alternative to palladium and, therefore, it attracts increasing attention from the researches. The present review is focused on the recent advances in the synthesis of N-heterocyclic carbene complexes of nickel and palladium and their application in catalysis of cross-coupling reactions of organic, organoelement and organometallic compounds with organic halides.     

Colloidal metal nanoparticles as a component of designed catalyst

Recent advances in the synthesis of colloidal metal nanoparticles of controlled sizes and shapes that are relevant for catalyst design are reviewed. Three main methods, based on colloid chemistry techniques in solution, i.e., chemical reduction of metal salt precursors, electrochemical synthesis, and controlled decomposition of organometallic compounds and metal-surfactant complexes, are used to synthesize metal nanoparticles. Their catalytic activity and selectivity depend on the shape, size and composition of the metal nanoparticles, and the support effect, as shown for many reactions in quasi-homogeneous and heterogeneous catalysis. A specially designed type of thermally stable catalysts--"embedded" metal catalysts, in which metal nanoparticles are isolated by porous support shells so that metal sintering is effectively avoided at high temperatures, are also introduced. The utilization of pre-prepared colloidal metal nanoparticles with tuned size, shape and composition as components of designed catalysts opens up new field in catalysis.     

同核铁系双金属络合物及其在均相催化体系中的应用

随着合成化学的不断发展,开发高活性催化剂来活化一些惰性化学键或者惰性分子受到越来越多的关注。双核金属络合物作为一类特殊的催化剂展现出了不同于单核金属催化剂的催化活性。在双核过渡金属催化体系中,因两个金属中心存在协同作用而表现出了独特的催化活性。铁、钴、镍为第四周期第VIII族元素,也称为铁系元素。该类金属廉价易得且参与的催化反应种类繁多,近年来引起了人们的广泛关注。本综述重点介绍了近年来同核双金属铁系络合物的合成及其表征。同时,对相关同核铁、钴以及镍催化剂在均相催化体系中的应用也进行了详细的介绍和总结。     

修饰型多相手性催化剂在不对称合成中的应用

本文评述了修饰型多相手性催化剂在不对称合成中的应用。按照不同的制备方法及催化反应对一些多相催化体系进行了归类总结, 包括过渡金属手性配合物的固相化、修饰型手性固体催化剂、手性分子筛及嵌入型粘土手性催化剂。对酒石酸及金鸡纳碱修饰型金属催化剂的反应机理也进行了探讨。     

Ionic liquid and solid HF equivalent amine-poly(hydrogen fluoride) complexes effecting efficient environmentally friendly isobutane-isobutylene alkylation

Isoparaffin-olefin alkylation was investigated using liquid as well as solid onium poly(hydrogen fluoride) catalysts. These new immobilized anhydrous HF catalysts contain varied amines and nitrogen-containing polymers as complexing agents. The liquid poly(hydrogen fluoride) complexes of amines are typical ionic liquids, which are convenient media and serve as HF equivalent catalysts with decreased volatility for isoparaffin-olefin alkylation. Polymeric solid amine:poly(hydrogen fluoride) complexes are excellent solid HF equivalents for similar alkylation acid catalysis. Isobutane-isobutylene or 2-butene alkylation gave excellent yields of high octane alkylates (up to RON = 94). Apart from their excellent catalytic performance, the new catalyst systems significantly reduce environmental hazards due to the low volatility of complexed HF. They represent a new, "green" class of catalyst systems for alkylation reactions, maintaining activity of HF while minimizing its environmental hazards.     

Encapsulation of a chiral MnIII(salen) complex in ordered mesoporous silicas: an approach towards heterogenizing asymmetric epoxidation catalysts for non-functionalized alkenes

Two immobilized chiral Mn^III(salen) complexes covalently anchored on modified MCM-41 (50 Å) and SBA-15 (75 Å) were prepared using 3-aminopropyltriethoxysilane as a reactive surface modifier to afford comparable or even higher enantioselectivity than homogeneous catalysts for the enantioselective epoxidation of a series of smaller to bulkier alkenes. The catalyst immobilized in silica with larger pore diameters was found to be more active. Compared to homogeneous catalysts, the heterogenized catalysts are more stable and can be recycled four times with retention of enantioselectivity.     

Polymer-bound metal complexes as catalysts: Synthesis, characterization, reactivity and catalytic activity in E-H bond activation

An account of recent research of our groups is presented, focusing on the preparation of several polystyrene anchored complexes and their use as catalysts in functionalization of alkenes. The procedures for covalently binding the ligands or ligand precursors are outlined, as well as for coordination of the metal ions. Instrumental techniques used for the characterization of the polymer-bound complexes have been highlighted. The heterogenized complexes are used as catalysts for the functionalization of alkenes, namely for oxidative aminations, hydroaminations and several types of oxidations, and results obtained using the catalysts prepared are presented. The main advantages of the use of the prepared supported catalyst are specified, namely their recyclability and their higher activity, also confirmed in many cases by comparison with their homogeneous counterparts. An account of the success in the use of EPR to characterize the V^IVO- and Cu^II-systems is also given.     

Asymmetric synthesis of organometallic reagents using enzymatic methods

The use of enzymatic catalysis in the synthesis and resolution of organometallic complexes is reviewed and discussed. Examples show the potential of biological catalysts for oxidation, reduction, hydrolysis, and esterification of both transition metal and main group organometallic substrates. Chirality in organometallic complexes caused by the presence of chiral carbon centers in substituent groups, tetrahedral or pseudotetrahedral metal centers, and planes of asymmetry can all be recognized by whole cell or isolated enzyme catalysts. Biocatalysts that achieve high levels of kinetic resolution are described. Other catalysts that produce high levels of asymmetric induction in reactions of a prochiral substrate are also described.     

Water-Soluble Ligands,Metal Complexes,and Catalysts: Synergism of Homogeneous and Heterogeneous Catalysis

Rapid developments in the field of catalysis are leading to an increased demand for tailor-made catalysts. Water-soluble complex catalysts, which are being intensively investigated at the present time, combine the advantages of homogeneous and heterogeneous catalysis: simple and complete separation of the product from the catalyst, high activity, and high selectivity. From the large number of available water-soluble ligands, the appropriate catalysts can be developed for many reactions. The industrial applications in the fields of hydrogenation and hydroformylation have already indicated the wide scope of this type of catalyst. In addition, the annual production of 300 000 tons of butyraldehyde through application of water-soluble rhodium complexes at Hoechst AG in Oberhausen, Germany, has demonstrated the industrial importance of the concept of complex-catalyzed reactions in aqueous two-phase systems. The efficient operation of catalytic processes increasingly requires the loss-free recycling of the noble metal catalyst, and this can be simply and economically realized in two-phase systems. Special applications in biochemical problems open up developments in the field of water-soluble transition metal complexes that far transcend the familiar kinds of homogeneous catalysis. In the near future, the investigation and application of metal complex catalysts that are compatible with the physiological, cheap, and environmentally friendly solvent, water, is likely to become a high priority in catalysis research.     

Immobilization of a Pd(II) complex on hydrophilic graphite oxide and its catalytic investigation in the Heck coupling reaction

Tetraamminepalladium(II) chloride monohydrate was heterogenized on hydrophilic graphite oxide (GO), synthesized by Brodie's method. Two samples, with Pd contents of 2% and 5%, referred to as Pd2 and Pd5, respectively, were prepared by a simple and scalable impregnation method and tested as catalysts in the Heck coupling reaction of styrene and bromobenzene. The reactions were carried out at 423 K for 3 hr by applying Na₂CO₃ as a base and N-methylpirrolidone or dimethylformamide (DMF) as a solvent. The Pd complexes heterogenized on graphene oxide platelets proved to be highly active and selective catalysts, and Pd2 was more efficient than Pd5. The effect of quaternary ammonium salts (tetrabutylammonium bromide and tetrabutylammonium chloride, TBAC) as modifiers and that of an ionic liquid (1-butyl-3-methylimidazolium bromide, bmim) was studied and the highest conversions were obtained when TBAC was employed. The selectivity for the formation of the main product, E-stilbene, was in the range 91–96%. Catalyst recycling was investigated and the extent of leaching was found to depend on the solvent. DMF proved to be a highly feasible reaction medium because both catalysts could be recycled five times in this solvent without any significant loss of activity. A hot filtration test was performed and gave evidence that leaching of the active Pd species did not take place under the above reaction conditions. These results substantiate the fact that simple cationic Pd species can be efficiently immobilized on pristine GO surfaces without the requirement of the functionalization of GO with nitrogen-containing mono or multidentate ligands as binding sites.     

Leveraging Metal and Ligand Reactive Sites for One Pot Reactions: Ligand-Centered Borenium Ions for Tandem Catalysis with Palladium

Tandem catalysts that perform two different organic transformations in a single pot are highly desirable because they enable rapid and efficient assembly of simple organic building blocks into more complex molecules. Many examples of tandem catalysis rely on metal-catalyzed reactions involving one or more metal complexes. Remarkably, despite surging interest in the development of chemically reactive (i. e., non-innocent) ligands, there are few examples of metal complexes that leverage ligand-centered reactivity to perform catalytic reactions in tandem with separate catalytic reactions at the metal. Here we report how multifunctional Pd complexes with triaminoborane-derived diphosphorus ligands, called TBDPhos, appear to facilitate borenium-catalyzed cycloaddition reactions at the ligand, and Pd-catalyzed Stille and Suzuki cross-coupling reactions at the metal. Both transformations can be accessed in one pot to afford rare examples of tandem catalysis using separate metal and ligand catalysis sites in a single complex.     

Recyclable Catalysts for Alkyne Functionalization

In this review, we present an assessment of recent advances in alkyne functionalization reactions, classified according to different classes of recyclable catalysts. In this work, we have incorporated and reviewed the activity and selectivity of recyclable catalytic systems such as polysiloxane-encapsulated novel metal nanoparticle-based catalysts, silica–copper-supported nanocatalysts, graphitic carbon-supported nanocatalysts, metal organic framework (MOF) catalysts, porous organic framework (POP) catalysts, bio-material-supported catalysts, and metal/solvent free recyclable catalysts. In addition, several alkyne functionalization reactions have been elucidated to demonstrate the success and efficiency of recyclable catalysts. In addition, this review also provides the fundamental knowledge required for utilization of green catalysts, which can combine the advantageous features of both homogeneous (catalyst modulation) and heterogeneous (catalyst recycling) catalysis.