It is possible to say that zeolites are the most widely used catalysts in industry They are crystalline microporous materials which have become extremely successful as catalysts for oil refining, petrochemistry, and organic synthesis in the production of fine and speciality chemicals, particularly when dealing with molecules having kinetic diameters below 10 A The reason for their success in catalysis is related to the following specific features of these materials:1 (1) They have very high surface area and adsorption capacity (2) The adsorption properties of the zeolites can be controlled, and they can be varied from hydrophobic to hydrophilic type materials (3) Active sites, such as acid sites for instance, can be generated in the framework and their strength and concentration can be tailored for a particular application (4) The sizes of their channels and cavities are in the range typical for many molecules of interest (5-12 A), and the strong electric fields2 existing in those micropores together with an electronic confinement of the guest molecules3 are responsible for a preactivation of the reactants (5) Their intricate channel structure allows the zeolites to present different types of shape selectivity, ie, product, reactant, and transition state, which can be used to direct a given catalytic reaction toward the desired product avoiding undesired side reactions (6) All of these properties of zeolites, which are of paramount importance in catalysis and make them attractive choices for the types of processes listed above, are ultimately dependent on the thermal and hydrothermal stability of these materials In the case of zeolites, they can be activated to produce very stable materials not just resistant to heat and steam but also to chemical attacks Avelino Corma Canos was born in Moncofar, Spain, in 1951 He studied chemistry at the Universidad de Valencia (1967−1973) and received his PhD at the Universidad Complutense de Madrid in 1976 He became director of the Instituto de Tecnologia Quimica (UPV-CSIC) at the Universidad Politecnica de Valencia in 1990 His current research field is zeolites as catalysts, covering aspects of synthesis, characterization and reactivity in acid−base and redox catalysis A Corma has written about 250 articles on these subjects in international journals, three books, and a number of reviews and book chapters He is a member of the Editorial Board of Zeolites, Catalysis Review Science and Engineering, Catalysis Letters, Applied Catalysis, Journal of Molecular Catalysis, Research Trends, CaTTech, and Journal of the Chemical Society, Chemical Communications A Corma is coauthor of 20 patents, five of them being for commercial applications He has been awarded with the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) 2373 Chem Rev 1997, 97, 2373−2419

From Microporous to Mesoporous Molecular-Sieve Materials and Their Use in Catalysis

Pick your Pd partners: A number of catalytic systems have been developed for palladium-catalyzed CH activation/CC bond formation. Recent studies concerning the palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed.

In the past decade, palladium-catalyzed CH activation/CC bond-forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming CC bonds from CH bonds: PdII/Pd0, PdII/PdIV, Pd0/PdII/PdIV, and Pd0/PdII catalysis. A more detailed discussion is then directed towards the recent development of palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle. Despite the progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge.

/pdf/palladium-ii-catalyzed-c-h-activation-c-c-cross-coupling-2546yox1wp.pdf

Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.

Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds

http://www1.udel.edu/chem/polenova/PDF/Polyoxometalates/POMs_Catalysis_NMR_ChemRev1998.pdf

Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

Oxidation of Unsaturated Hydrocarbons by Pd(O‐Ac)2 Using a Molybdovanadophosphate/Dioxygen System

Aerobic oxidation of primary alcohols to aldehydes was efficiently performed using a Ru(PPh 3 ) 3 Cl 2 /hydroquinone system under atmospheric oxygen at 60 °C. A primary alcohol even in the presence of a secondary one was selectively oxidized to the corresponding aldehyde in high yield.

Selective Aerobic Oxidation of Primary Alcohols Catalyzed by a Ru(PPh3)3Cl2/Hydroquinone System.

The reaction of various ethers with alkenes bearing an electron-withdrawing substituent in the presence of N -hydroxyphthalimide combined with Co(OAc) 2 under dioxygen produced the corresponding adducts in which oxygen is incorporated to alkenes in good yields. Oxcetane, furan and pyrane smoothly added to ethyl fumarate even at room temperature to give coupling products in high yields. An acyclic ether like dibutyl ether also added to fumarate under mild conditions to give a hydroxylated adduct in satisfactory selectivity.

Radical Addition of Ethers to Alkenes under Dioxygen Catalyzed by N‐Hydroxyphthalimide (NHPI)/Co(OAc)2.

Oxidation of the olefins (I) or the allylic alcohols (III) with the complex molybdatophosphate PCMP produces the oxiranes (II) or (IV).

Oxidation of Olefins and Alcohols by Peroxomolybdenum Complex Derived from Tris(cetylpyridinium) 12-Molybdophosphate and Hydrogen Peroxide.

Nitrotoluenes are efficiently oxidized with air to the corresponding nitrobenzoic acids by the use of N -acetoxyphthalimide (NAPI) as a key catalyst. Thus, p - and m -nitrotoluenes under 10 atm of air in the presence of NAPI combined with Co(OAc) 2 (0.5 mol%) and Mn(OAc) 2 (0.05 mol%) at 130°C afforded p - and m -nitrobenzoic acids in 81 and 92% yields, respectively. o -Nitrotoluene was oxidized to o -nitrobenzoic acid in 51% yield by the aid of NO 2 .

Yasutaka Ishii

Papers

Oxidation of Unsaturated Hydrocarbons by Pd(O‐Ac)2 Using a Molybdovanadophosphate/Dioxygen System

Selective Aerobic Oxidation of Primary Alcohols Catalyzed by a Ru(PPh3)3Cl2/Hydroquinone System.

Radical Addition of Ethers to Alkenes under Dioxygen Catalyzed by N‐Hydroxyphthalimide (NHPI)/Co(OAc)2.

Oxidation of Olefins and Alcohols by Peroxomolybdenum Complex Derived from Tris(cetylpyridinium) 12-Molybdophosphate and Hydrogen Peroxide.

Oxidation of Nitrotoluenes with Air Using N‐Hydroxyphthalimide Analogues as Key Catalysts.