In one aspect, the disclosure relates to a mode of asymmetric induction in radical processes based on enhanced hydrogen-bonding capability and the situation of metal centers in cavity-like chiral environments. Also disclosed is an asymmetric system for stereoselective synthesis of cyclopropane and aziridine derivatives. The disclosed Co(II)-based metalloradical system has been shown to have an unusual capability of controlling both the degree and sense of asymmetric induction in cyclopropanation and aziridination reactions in a systematic manner. The disclosed system is applicable to a broad scope of substrates having diazo or azido moieties and exhibits a remarkable profile of reactivity and selectivity, providing access to cyclopropane diastereomers and aziridine enantiomers in highly enantioenriched forms. Also disclosed are catalysts useful in the disclosed processes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

Surface hydroxyl groups on porous and nonporous metal oxides, such as silica gel and alumina, were metalated with catalyst precursors, such as complexes of earth abundant metals (e.g., Fe, Co, Cr, Ni, Cu, Mn and Mg). The metalated metal oxide catalysts provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of organic transformations. The catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

In one aspect, the disclosure relates to a mode of asymmetric induction in radical processes based on sequential combination of enantiodifferentiative H-atom abstraction and stereoretentive radical substitution. Also disclosed is an asymmetric system for stereoselective synthesis of strained 5-membered cyclic sulfamides via radical 1,5-CH amination of sulfamoyl azides. The disclosed metalloradical system can control the degree and sense of asymmetric induction in the catalytic radical CH amination in a systematic manner. The disclosed system is applicable to a broad scope of substrates with different types of C(sp.sup.3)-H bonds and exhibits reactivity and selectivity, providing access to both enantiomers of useful 5-membered cyclic sulfamides in a highly enantioenriched form. Also disclosed are catalysts useful in these processes. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

The present invention relates to the field of polymerisation catalysts, and systems comprising these catalysts for polymerising carbon dioxide and an epoxide, a lactide and/or lactone, and/or an epoxide and an anhydride. The catalyst is of formula (I): ##STR00001##
wherein at least one of M.sub.1 or M.sub.2 is selected from Ni(II) and Ni(III)-X. A process for the reaction of carbon dioxide with an epoxide; an epoxide and an anhydride; and/or a lactide and/or a lactone in the presence of the catalyst is also described.

A polyvinyl alcohol is produced in a method comprising: a polymerization step comprising polymerizing vinyl ester monomers by controlled radical polymerization in the presence of a radical initiator and an organic cobalt complex to obtain a polymer solution containing a polyvinyl ester; an extraction step comprising extracting a cobalt complex from the polymer solution by contacting an aqueous solution containing a water-soluble ligand with the polymer solution; and a saponification step comprising saponifying the polyvinyl ester after the extraction step to obtain a polyvinyl alcohol. A method for producing a polyvinyl alcohol is thus provided that has a narrow molecular weight distribution and a high number-average molecular weight with good hue and further good solubility in water.

A method of utilizing a catalytic complex having a transition metal (e.g. nickel, cobalt) ion coordinated to a calixarene ligand in upgrading hydrocarbon feedstocks containing C.sub.20 through C.sub.50 hydrocarbons (e.g. vacuum gas oil) to produce light petroleum products (e.g. medium distillate, naphtha) is specified. A method of using the catalytic complex with a supported co-catalyst to synergistically hydrocrack the feedstocks is also provided.

The porphyrin-based catalysts for water splitting are composites of porphyrin or metalloporphyrin active ingredients, conductive carbon (e.g., graphene sheets, vapor grown carbon fiber, carbon black, etc.), and a polymer or binder that may be coated on a glassy carbon electrode. The polymer or binder may be Nafion oil or polyvinylidine difluoride. The porphyrin may be a porphyrin having a transition metal or hydrogen at its center, and may be halogenated and/or have a thiophene substituent.

Metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds, and their preparation method and applications in catalyzing the degradation of chemical warfare agent simulants. In the synthesis, Na.sub.2MoO.sub.4, p-hydroxybenzonic acid (PHBA), alanine (Ala), KCl, transition metal cations and As.sub.2O.sub.3 as raw materials and water are used as solvent. At room temperature, 2-chloroethyl ethyl sulfide (CEES) and the prepared polyoxometalate hybrid compounds were mixed together in anhydrous ethanol and stirred, and H.sub.2O.sub.2 was subsequently added into the reaction system. The catalytic reaction for the degradation of CEES was finished within 5 min under stirring. In the catalytic hydrolysis of diethyl cyanophosphonate (DECP), the catalyst, DECP, DMF and H.sub.2O were put together and mixed fully. The prepared polyoxometalate hybrid compounds have the advantages of high conversion, high selectivity and easy recyclability in catalyzing the degradation of two types of chemical warfare agent simulant.

The invention relates to a process for the metathesis of olefins implemented with a catalyst comprising a mesoporous matrix and at least the elements molybdenum and silicon, said elements being incorporated into said matrix by means of at least one precursor comprising molybdenum and silicon and having at least one sequence of SiOMo bonds.

The present invention discloses a process for the photocatalytic splitting of water using self-assembled metalloporphyrin 2D-sheet of formula (I) to form hydrogen and oxygen.