Provided is a material that, when compared with SAPd, exhibits the similar activity in cross-coupling (CC) reactions, can decrease the amount of catalytic metal that is mixed into the reaction product, and increases the number of times use can be repeated. Provided are a catalyst and a catalyst precursor that use a catalytic metal other than Pd and that exhibit the CC reaction activity similar to when Pd is used. Provided are a catalyst and a catalyst precursor that exhibit the similar CC reaction activity when using Pd or a catalytic metal other than Pd, without using a carrier such as metal and without using piranha solution. A composite wherein catalytic metal nanoparticles are dispersed in a continuous phase comprising a polymer having C2-6 alkylene group units and phenylene group units (an alkylene group unit being bonded to at least the first and fourth position of the phenylene group unit). The particle diameter of the catalytic metal nanoparticles is at most 20 nm. A composite structure including a substrate, and the aforementioned composite provided to the surface of the substrate. A method for manufacturing the composite structure by dehydrocondensating, in the presence of a catalytic metal compound, a benzene compound having at least two alkyl groups (two of the alkyl groups being at the first and fourth position) in order to form the composite on the substrate surface.

Reactions that directly install nitrogen into CH bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Selective intramolecular CH amination reactions that achieve high levels of reactivity, while maintaining excellent site-selectivity and functional-group tolerance is a challenging problem. Herein is reported a manganese perchlorophthalocyanine catalyst [Mn.sup.III(ClPc)] for intermolecular benzylic CH amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site-selectivity. In the presence of Brnsted or Lewis acid, the [Mn.sup.III(ClPc)]-catalyzed CH amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies indicate that CH amination proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where CH cleavage is the rate-determining step of the reaction. Collectively these mechanistic features contrast previous base-metal catalyzed CH aminations.

The present disclosure relates to a metal catalyst for CH bond activation and/or CN coupling reaction, and a method using the same and application thereof. Specifically, a metal catalyst represented by the following formula:

##STR00001##

wherein
Q is a 5 or 6 membered aromatic ring;
W, X, and Y are the same or different, and are independently N, S, P, or O;
M is Ni, Pd, Fe, Co, Cr, Mn, Cu, Pt, Ir, or Ru;
Z is halide (F, Cl, Br, or I), acetate, water, or hydroxyl;
R.sub.1 and R.sub.2 are the same or different, and are independently alkyl, aryl, alkylaryl or cycloalkyl.

The present invention provides a complex of formula (1),

##STR00001##

wherein, M is palladium or nickel, R.sub.1 and R.sub.2 are independently organic groups having 1-20 carbon atoms, or R.sub.1 and R.sub.2 are linked to form a ring structure with the phosphorus atom, R.sub.3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R.sub.4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, and X is an anionic ligand. The invention also provides a process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions.

A complex of formula (1), ##STR00001##
wherein, M is palladium or nickel, R.sub.1 and R.sub.2 are independently organic groups having 1-20 carbon atoms, or R.sub.1 and R.sub.2 are linked to form a ring structure with the phosphorus atom, R.sub.3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R.sub.4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, X is an anionic ligand. A process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions is also provided.

This disclosure relates to synthetic coupling methods using catalytic molecules. In certain embodiments, the catalytic molecules comprise heterocyclic thiolamide, S-acylthiosalicylamide, disulfide, selenium containing heterocycle, diselenide compound, ditelluride compound or tellurium containing heterocycle. Catalytic molecules disclosed herein are useful as catalysts in the transformation of hydroxy group containing compounds to amides, esters, ketones, and other carbon to heteroatom or carbon to carbon transformations.

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd.sub.3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd.sub.3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.

The present invention relates to a novel class of benzimidazolyl/imidazolyl phosphine ligands, methods of preparing such ligands via a simple one-pot protocol, and applications of the ligands in catalytic reactions.

Disclosed herein are embodiments of a Pd(0) precursor complex and embodiments of phosphorus-based Pd(0) catalysts formed therefrom. Also disclosed are method embodiments for making the Pd(0) precursor complex and the phosphorus-based Pd(0) catalysts. The Pd(0) precursor complex can be used to generate, in situ, the phosphorus-based Pd(0) catalysts, in various different types of palladium-mediated coupling reactions.

Provided herein are nickel(O) catalysts that are stable when exposed to air and can be used to catalyze the formation of a CC, CO, or CN bond.