Heterocycle-amine ligands, compositions, complexes, and catalysts

A metal-ligand complex characterized by the formula:

• wherein
• M is a metal selected from the group consisting of groups 3-6 and lanthanides of the periodic table of elements;
• R1 is an optionally substituted hydrocarbyl or heteroatom containing hydrocarbyl;
• T is a bridging group;
• X1 is nitrogen, phosphorus, or —C(R4)n′—, X2 and X3 are independently selected from the group consisting of oxygen, sulfur, —C(R4)n′—, —N(R4)n″—, and —P(R4)n″—, and X4 is —N(R4′)—, —P(R4′)—, or —C(R4′)(R4)n″—, where each R4 is independently selected from the group consisting of hydrogen, halogen, nitro, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, and combinations thereof, and each R4′ is selected from the group consisting of optionally substituted aryl and heteroaryl, and X5′ is oxygen or sulfur, each n′ is 1 or 2, and each n″ is 0 or 1, provided that optionally, two or more R1, R2, R3, R4 or R4′ groups may be joined to form one or more optionally substituted fused ring systems;
• x is 1 or 2;
• each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof, provided that optionally, two or more L groups are joined into a ring structure and that one or more of the ligands L may be ionically bonded to the metal M;
• and
• m′ is 1, 2, 3, or 4.

A metal complex characterized by the formula:

• wherein
• M is a metal selected from the group consisting of groups 3-6 and lanthanides of the periodic table of elements;
• R1 is optionally substituted hydrocarbyl or heteroatom containing hydrocarbyl;
• T is a bridging group;
• J′ is an optionally substituted heterocyclic group containing a five-membered heterocycle, the five-membered heterocycle including at least one but no more than four heteroatoms and including a nitrogen, phosphorus, oxygen, sulfur, or carbene in a ring position adjacent to the ring atom bonded to T, wherein J′ includes 2 atoms bonded to the metal M, one of the 2 atoms being the nitrogen, phosphorus, oxygen, sulfur, or carbene in the ring position adjacent to the ring atom bonded to T, and being bonded to M via a dative bond, and the other of the 2-atoms being bonded to the metal M through a covalent bond;
• and
• each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof, provided that optionally, two or more L groups are joined into a ring structure and that one or more of the ligands L may be ionically bonded to the metal M, and m′ is 1, 2 3, or 4.

A metal-ligand complex characterized by the formula

• wherein:
• M is a metal selected from the group consisting of groups 3-6 and lanthanides of the periodic table of elements;
• A is an optionally substituted metallocycle containing five, six or seven atoms in the ring, including M;
• B is an optionally substituted metallocycle containing five or six atoms in the ring, including M;
• C is an optionally substituted five-membered heterocycle, wherein X1 and X4 are selected from the group consisting of nitrogen, phosphorus, and —C(R4)n″—, X2 and X3 are selected from the group consisting of oxygen, sulfur, —C(R4)n′—, —N(R4)n″—, and —P(R4)n″—, and X5 is nitrogen, carbon, oxygen, phosphorus, or sulfur, n′ is 1 or 2, and n″ is 0 or 1;
• R1 is optionally substituted hydrocarbyl or heteroatom containing hydrocarbyl;
• each R4, R26 and R27 is independently selected from the group consisting of hydrogen, halogen, and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, and combinations thereof, r is 1, 2, 3 or 4, r′ is 1, 2, 3, or 4, provided that optionally any combination of two or more R4, R26 and/or R27 groups may be joined together to form one or more optionally substituted fused ring systems;
• each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof, provided that optionally, two or more L groups are joined into a ring structure and that one or more of the ligands L may be ionically bonded to the metal M, and m′ is 1, 2, 3 or 4.