This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

Non-d.sup.0 rhenium(V) alkylidyne catalysts useful for catalyzing alkyne metathesis reactions, such as homo- and cross-metathesis of alkynes or diynes, ring closing metathesis and ring-opening metathesis, methods or use, and preparation thereof. The catalysts are stable to air and moisture and tolerate a variety of functional groups in substrates.

The disclosure provides Group 6 complexes, which, in some embodiments, are useful for catalyzing olefin metathesis reactions. In some embodiments, the compounds are compounds of the following formula:

##STR00001##

wherein: M is a Group 6 metal atom; X is an oxygen atom, ═N—R.sup.5, ═N—N(R.sup.5)(R.sup.5′) or ═N—O—R.sup.5, R.sup.5 and R.sup.5′ independently being various substituents, such as aryl or heteroaryl, each optionally substituted; n is 0 or 1; R.sup.z is a neutral ligand; R.sup.1 is hydrogen or an organic substituent; R.sup.2 is an aryl or heteroaryl group, each optionally substituted; R.sup.3 is an anionic ligand; and R.sup.4 is an anionic ligand, such as a pyrrolide, a pyrazolide, an imidazolide, an indolide, an azaindolide, or an indazolide, each optionally substituted.

A tetraanionic OCO pincer ligand metal-oxo-alkylidene complex is prepared from a trianionic pincer ligand supported metal-alkylidyne. The metal can be tungsten or other group 5-7 transition metal. The tetraanionic pincer ligand metal-oxo-alkylidene complex, a trianionic OCO pincer ligand metal complex, or a trianionic ONO pincer ligand metal complex can be used to polymerize cycloalkenes. The poly(cycloalkene)s are predominantly cis-alkene macrocyclics.

A tetraanionic OCO pincer ligand metal-oxo-alkylidene complex is prepared from a trianionic pincer ligand supported metal-alkylidyne. The metal can be tungsten or other group 5-7 transition metal. The tetraanionic pincer ligand metal-oxo-alkylidene complex, a trianionic OCO pincer ligand metal complex, or a trianionic ONO pincer ligand metal complex can be used to polymerize cycloalkenes. The poly(cycloalkene)s are predominantly cis-alkene macrocyclics.

Disclosed is a method for preparing a borate ester on the basis of a tricyclopentadienyl rare earth metal complex, the method comprising the following steps: uniformly stirring and mixing a catalyst, a borane and a carbonyl compound for reaction to prepare a borate ester, wherein the catalyst is a tricyclopentadienyl rare earth metal complex; and the molecular formula of the tricyclopentadienyl rare earth metal complex can be expressed as: Ln(Cp).sub.3, wherein Ln represents a rare metal selected from one of lanthanide elements. The preparation method has a higher catalytic activity, mild reaction conditions, a product that is easy to post-treat, a short reaction time, a low catalyst consumption amount, and a good range of applicable substrates, and can be used for industrial production.

The disclosure provides Group 6 complexes, which, in some embodiments, are useful for catalyzing olefin metathesis reactions. In some embodiments, the compounds are compounds of the following formula: ##STR00001##
wherein: M is a Group 6 metal atom; X is an oxygen atom, ═N—R.sup.5, ═N—N(R.sup.5)(R.sup.5′) or ═N—O—R.sup.5, R.sup.5 and R.sup.5′ independently being various substituents, such as aryl or heteroaryl, each optionally substituted; n is 0 or 1; R.sup.z is a neutral ligand; R.sup.1 is hydrogen or an organic substituent; R.sup.2 is an aryl or heteroaryl group, each optionally substituted; R.sup.3 is an anionic ligand; and R.sup.4 is an anionic ligand, such as a pyrrolide, a pyrazolide, an imidazolide, an indolide, an azaindolide, or an indazolide, each optionally substituted.

The invention relates to a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i): (i) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction such that the molar ratio of said compound to the first or the second olefin is from 1:500 or less, and the conversion of the first or the second olefin to said olefin is at least 50%, characterized in that as compound that catalyzes said metathesis reaction a compound of the following formula is used: ##STR00001## wherein M is Mo or W; R.sup.1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted; R.sup.2 and R.sup.3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R.sup.5 is alkyl, alkoxy, heteroalkyl, aryl, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R.sup.4 is a residue R.sup.6—X—, wherein X═O and R.sup.6 is aryl, optionally substituted; or X═S and R.sup.6 is aryl, optionally substituted; or X═O and R.sup.6 is (R.sup.7, R.sup.8, R.sup.9)Si; wherein R.sup.7, R.sup.8, R.sup.9 are alkyl or phenyl, optionally substituted; or X═O and R.sup.6 is (R.sup.10, R.sup.11, R.sup.12)C, wherein R.sup.10, R.sup.11, R.sup.12 are independently selected from phenyl, alkyl; optionally substituted; and to the catalysts used in the method.

Disclosed herein are mono- and di-substituted tetrazines and methods of their preparation and converting an oxetanyl ester to a thio-substituted tetrazine, which is then converted to a mono-substituted tetrazine, a di-substituted tetrazine, or a vinylether disubstituted tetrazine.

Embodiments in accordance with the present invention encompass a two component composition containing in one component a latent organo-ruthenium carbide catalyst, and in another component a photoactive acid generator or a thermally active acid generator, and either of the components containing a mixture of photoactive compound along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said components are mixed together and exposed to a suitable radiation (or heat) to form a three-dimensional (3D) object. The three-dimensional objects so formed exhibits improved mechanical properties, particularly, high heat distortion temperature, impact strength, elongation to break, among others. Accordingly, compositions of this invention are useful as 3D inkjet materials for forming high impact strength objects of various sizes with microscale features lower than 100 microns, among various other uses.