The present invention refers to novel ruthenium- and osmium-based catalysts for olefin metathesis reactions, particularly to catalysts having stereoselective properties. Z-selectivity is obtained by utilizing two mono-anionic ligands of very different steric requirement. In olefin metathesis reactions these catalysts selectively provide the Z-isomer of disubstituted olefinic products even in presence of air or of acids.

Embodiments in accordance with the present invention encompass compositions encompassing a latent organo-ruthenium compound, a pyridine compound, a photosensitizer and an ultra violet light blocking compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to suitable actinic radiation to form a substantially transparent film or a three dimensional object. Surprisingly, the compositions are very stable at ambient conditions to temperatures up to 80° C. for several days and undergo mass polymerization only when subjected to actinic radiation under inert atmosphere such as for example a blanket of nitrogen. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as 3D printing materials, coatings, encapsulants, fillers, leveling agents, among others.

It is an object of the present invention to provide an organometallic complex that can emit phosphorescence. In the following general formula (G1), X represents —O— or —N(R.sup.10)—. R.sup.1 to R.sup.9 each represent any of hydrogen, an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, a halogen group, a haloalkyl group, and an aryl group having 6 to 12 carbon atoms. In addition, R.sup.10 represents any of an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a heteroaryl group having 4 to 10 carbon atoms. Moreover, M represents an element belonging to Group 9 or 10. ##STR00001##

Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. ##STR00001## In formula (1), R.sup.1-R.sup.6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R.sup.1-R.sup.3 and one of R.sup.4-R.sup.6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO and phosphine. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.

The present invention relates to novel Ruthenium complexes of formulae A1-A4 and their use, inter alia, for (1) dehydrogenative coupling of alcohols to esters; (2) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (3) preparing amides from alcohols and amines—(including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or polymerization of amino alcohols and/or forming cyclic dipeptides from p-aminoalcohols; (4) hydrogenation of amides (including cyclic dipeptides, polypeptides and polyamides) to alcohols and amines; (5) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (6) dehydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water and a base to form carboxylic acids; and (10) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. The present, invention further relates to the use of certain known Ruthenium complexes for the preparation of amino acids or their salts from amino alcohols.

The invention relates to a ruthenium alkylidene complex comprising a 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligand, the cycloalkyl group of said 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligand being a cyclic secondary aliphatic alkyl.

Disclosed are methods for the preparation of ligands for complexes, methods for preparing complexes and complexes having those ligands. Also provided is the use of a complex as a catalyst in a method of synthesis.

Backfunctionalized imidazolinium salts and methods of synthesizing the same and NHC carbene-metal complexes therefrom. For backfunctionalized imidazolinium salts of the formula:

##STR00001##

Wherein R.sup.1 is selected from the group consisting of an ester group, an amide group, and an aromatic group; R.sup.2 is selected from the group consisting of hydrogen, an ester group, an amide group, and an aromatic group; R.sup.3 and R.sup.4 are each an aliphatic group; and
X is an anion; the method comprises cyclization of a halogenated acrylate with Hünig's base in a solvent.

The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost-effective manner. The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.

There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.