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.

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.

Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.

A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.

In one aspect, the invention provides a method for synthesizing a fatty olefin derivative. The method includes: a) contacting an olefin according to Formula I ##STR00001##
with a metathesis reaction partner according to Formula IIb ##STR00002##
in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula IIIb: ##STR00003##
and
b) converting the metathesis product to the fatty olefin derivative. Each R.sup.1 is independently selected from H, C.sub.1-18 alkyl, and C.sub.2-18 alkenyl; R.sup.2b is C.sub.1-8 alkyl; subscript y is an integer ranging from 0 to 17; and subscript z is an integer ranging from 0 to 17. In certain embodiments, the metathesis catalyst is a tungsten catalyst or a molybdenum catalyst. In various embodiments, the fatty olefin derivative is a pheromone. Pheromone compositions and methods of using them are also described.

Described herein are heterogeneous catalysts for removing impurities, such as halogen oxyanions (e.g., ClO.sub.4.sup.− and ClO.sub.3.sup.−), from a fluid, the catalyst can comprise: an oxygen atom transfer (OAT) transition metal, a Group VIII metal, and a support, where the transition metal, and the Group VIII metal can be in physical communication with the support either directly or indirectly through each other, whereby the catalyst can chemically remove impurities from the fluid. Certain embodiments provide catalysts that further comprise nitrogen donor ligand(s). Accordingly, such catalysts that comprise the OAT transition metal in the form of a complex with one or more nitrogen donor ligands have enhanced efficiency in reducing halogen oxyanion (e.g., ClO.sub.4.sup.−) to Cl.sup.−. Also described are methods or kits for making the catalysts and methods or reactor for the treatment of a fluid utilizing the catalyst.

Compositions can include compounds having a formula: Co.sub.yW.sub.1-xMx0.sub.4 (I), wherein M is Mo, V, or Nb; 0.5≥x≥0; and 1<y≤4; and wherein the compound has an X-ray powder diffraction pattern including characteristic diffraction peaks having d-spacing values of about 2.90 Å, 2.56 Å, and 1.73 Å. Methods can include making a bulk catalyst composition including (i) combining tungstic acid and cobalt carbonate and (ii) reacting the tungstic acid and cobalt carbonate to form a catalyst composition, wherein the cobalt carbonate has an X-ray powder diffraction pattern including characteristic diffraction peaks having d-spacing values of about 10.03 Å, 5.91 Å, 4.35 Å, and 4.21 Å.

A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.