The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

Supported catalysts include a solid support, a metal-ligand complex tethered to a surface of the solid support through at least two surface reactive moieties of the metal-ligand complex, and a conformationally stable molecular pore defined between the metal-ligand complex and the surface of the solid support. The metal-ligand complex includes a catalytic metal center, such as a transition metal, coordinated with multiple monodentate ligands, a multidentate ligand, or a combination thereof. The ligands include a tethering portion that is terminated by a surface reactive moiety tethered to the surface of the solid support by a surface interaction. By tailoring the tethering portion, a volume of the molecular pore may be provided that is selective and suitable for a chosen reactant or a chosen reaction type.

Supported chromium catalysts with an average valence less than +6 and having a hydrocarbon-containing or halogenated hydrocarbon-containing ligand attached to at least one bonding site on the chromium are disclosed, as well as ethylene-based polymers with terminal alkane, aromatic, or halogenated hydrocarbon chain ends. Another ethylene polymer characterized by at least 2 wt. % of the polymer having a molecular weight greater than 1,000,000 g/mol and at least 1.5 wt. % of the polymer having a molecular weight less than 1000 g/mol is provided, as well as an ethylene homopolymer with at least 3.5 methyl short chain branches and less than 0.6 butyl short chain branches per 1000 total carbon atoms.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst including a chromium compound coordinated with a ligand and a co-catalyst including an organoaluminum compound. The ligand may have a chemical structure: (R.sub.1)(R.sub.2)A-X—C(R.sub.3)(R.sub.4). A and C may be phosphorus. X may be B(R.sub.5), Si(R.sub.5).sub.2, N(R.sub.5), wherein R.sub.5 is an aryl group substituted with a halogen, halogenated alkyl or a silyl group, and wherein B, or N, or Si is bound to A and C. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be independently chosen hydrocarbyl groups or heterohydrocarbyl groups.

A method for C—H bond activation and/or C—N coupling reaction comprises adding a hydrocarbon material to a container; adding a metal catalyst to the container; adding a primary or a secondary amine to the container. The metal catalyst is represented by the following formula:

##STR00001##

where 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); R1 and R2 are the same or different, and are independently alkyl, aryl, alkylaryl or cycloalkyl; and n is 1, 2, or 3.

Described herein are compositions composed of frustrated Lewis pairs impregnated in porous materials such as, for example, metal-organic frameworks, and their uses thereof. These compositions may allow new applications of frustrated Lewis pairs in catalysis by sequestering and protecting the frustrated Lewis pair within the nanospace of the porous material. Also provided are methods of hydrogenating an organic compound having at least one unsaturated functional group comprising using the compositions described herein.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more chlorinated hydrocarbons, chloro-aluminum alkyls, or combinations of these.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C.sub.2-C.sub.30) carboxylate, acetylacetonate, or a (C.sub.1-C.sub.30) hydrocarbyl; L.sub.1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C.sub.6-C.sub.20)fluorine-substituted aryl, a (C.sub.6-C.sub.20)fluorine-substituted aryloxy, or a (C.sub.1-C.sub.20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more polyether alcohols or one or more non-polymeric ethers.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst including a reaction product of a chromium compound and a ligand having the structure according to Formula (II). In Formula (II), A and C may be independently chosen from phosphorus, arsenic, antimony, bismuth, and nitrogen; B may be a linking group between A and C; and R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be independently chosen from a (C.sub.1-C.sub.50) hydrocarbyl or a (C.sub.1-C.sub.50) heterohydrocarbyl. The catalyst system may include a co-catalyst including a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more quaternary salts; one or more organic acids, organic acid salts, esters, anhydrides, or combinations of these; one or more chlorinated hydrocarbons, chloro-aluminum alkyls, or combinations of these; one or more polyether alcohols; or one or more non-polymeric ethers.

A catalyst composition including: (a) a chromium compound; (b) a ligand of the general structure (A) R.sub.1R.sub.2P—N(R.sub.3)—P(R.sub.4)—NR.sub.5R.sub.6 or (B) R.sub.1R.sub.2P—N(R.sub.3)—P(XR.sub.7)R.sub.8 or R.sub.1R.sub.2P—N(R.sub.3)—P(XR.sub.7).sub.2, with X═O or S,
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are independently C.sub.1-C.sub.10-alkyl, C.sub.6-C.sub.20-aryl, C.sub.3-C.sub.10-cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and (c) an activator or co-catalyst; and a process for tri- and/or tetramerization.