New Complexes of Ruthenium, Method for Their Preparation, and Their Application in Olefin Metathesis Reactions

摘要

The present invention provides new ruthenium complexes of Formula (1), which contain a chelate ring created by a halogen atom X. The invention concerns also a method for the preparation of the new ruthenium complexes and their application in metathesis reactions.;

主权项

1. A complex of ruthenium with formula 1,wherein
L1 denotes an inert ligand; Z1 and Z2 denote, independently, an anion ligand; X denotes a halogen atom; R1 denotes an atom of hydrogen, a halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C3-C12 cycloalkenyl, C2-C12 alkynyl, C3-C12 cycloalkynyl, C1-C12 alkoxyl, C5-C20 aryl, C5-C20 heteroaryl, or 3-12-membered heterocycle; A denotes a bivalent radical selected from the group consisting of C1-C12 alkylene, C2-C12 alkenylene, C2-C12 alkynylene, C5-C20 arylene, and C5-C20 heteroarylene, wherein the C1-C12 alkylene, the C2-C12 alkenylene, the C2-C12 alkynylene, the C5-C20 arylene, and the C5-C20 heteroarylene may be optionally substituted with at least one functional group R2; each R2 functional group denotes, independently, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, —OR3, —SR3, —S(O)mR3, —SO2NR3R4, —S(O)2OR3, —NO2, —NO, —SCN, —NR3R4, —CN, —C(P)R3, —O(CR3R4)nR5, —NR3C(O)R4,—(CR3R4)nC(O)OR5, —(CR3R4)nOR5, —C(═NR3)NR4R5, —NR3C(0)NR4R5, —NR3S(O)pR4, —NC(═O)R3C(═O)R4, —NR3P(═O)R4R5, —NR3As(═O)R4R5, —PR3R4, —POR3R4, —POR3OR4, —P(═O)R3R4, —P(═O)OR3R4, —P(═O)OR3OR4, —AsR3R4, —AsOR3R4, —AsOR3OR4, —As(═O)R3R4, —As(═O)OR3R4, —As(═O)OR3OR4, —NR3—C(═NR4)NR5R6, —C(═O)R3, —C(═O)OR3, —C(═S)OR3, —C(═O)SR3, —C(═S)SR3, —C(═S)NR3R4, —SiR3R4R5, —SiOR3R4R5, —SiOR3OR4R5, —SiOR3OR4OR5, —(CR3R4)n(3-12-membered heterocycle), —(CR3R4)n(C3-C12 cycloalkyl), —(CR3R4)n(C5-C20 aryl), —(CR3R4)n(5-12-membered heteroaryl), —(CR3R4)nC(O)NR5R6, or —(CR3R4)nC(O)R5; and/or R2 groups with adjacent atoms may bond together, creating C5-C20 aryl or 3-12-membered heterocycle; and/or R2 groups with adjacent atoms may bond with the R1 group, creating C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements, wherein the C5-C20 aryl, indenylene, heteroindenylene, 3-12-membered heterocycle, and polycyclic or heteropolycyclic arrangements may be substituted with at least one functional group selected from the group consisting of a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, —OR3, —SR3, —S(O)mR3, —SO2NR3R4, —S(O)2OR3, —NO2, —NO, —SCN, —NR3R4, —CN, —C(O)R3, —O(CR3R4)nR5, —NR3C(O)R4, —(CR3R4)nC(O)OR5, —(CR3R4)nOR5, —C(═NR3)NR454, —NR3C(0)NR4R5, —NR3S(O)pR4, —NC(═O)R3C(═O)R4, —NR3P(═O)R4R5, —NR3As(═O)R4R5, —PR3R4, —POR3R4, —POR3OR4, —P(═O)R3R4, —P(═O)OR3R4, —P(═O)OR3OR4, —AsR3R4, —AsOR3R4, —AsOR3OR4, —As(═O)R3R4, —As(═O)OR3R4, —As(═O)OR3OR4, —NR3—C(═NR4)NR5R6, —C(═O)R3, —C(═O)OR3, —C(═S)OR3, —C(═O)SR3, —C(═S)SR3, —C(═S)NR3R4, —SiR3R4R5, —SiOR3R4R5, —SiOR3OR4R5, —SiOR3OR4OR5, —(CR3R4)n(3-12-membered heterocycle), —(CR3R4)n(C3-C12 cycloalkyl), —(CR3R4)n(C5-C20 aryl), —(CR3R4)n(5-12-membered heteroaryl), —(CR3R4)nC(O)NR5R6, and —(CR3R4)nC(O)R5; each functional group R3, R4, R5, and R6 denotes, independently, an atom of hydrogen, a halogen atom, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, C5-C20 aryl, or 5-12-membered heterocycle; each m denotes, independently, 0, 1, or 2; each n denotes, independently, 0, 1, 2, 3, or 4; and each p denotes, independently, 1 or 2.