Use of metal complexes having organic ligands for activating olefin metathesis ruthenium (pre)catalysts

A method, comprising:

• activating olefin metathesis ruthenium (pre)catalysts in a metathesis reaction using one of the following compounds;
• copper complexes having at least one organic ligand, or
• ruthenium complexes having at least one organic ligand;
• wherein the olefin metathesis ruthenium (pre)catalyst is described by a general formula 2, 3a, 3b, 3c 3d or 3e:
• wherein:
• each X1 and X2 is independently an anionic ligand selected from a halogen atom, —CN, —SCN, —OR′, —SR′, —O(C═O)R′, —O(SO2)R′ or —OSi(R′)3 group, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl or C5-C20 aryl, which may be independently substituted with one and/or more substituents selected from the group comprising C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• each R1 and R2 is independently a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perhaloalkyl, C2-C25 alkenyl, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl, C7-C24 aralkyl, C5-C24 perhaloaryl or a 3-12 membered heterocycle which may be independently substituted with one and/or more substituents selected from the group comprising a hydrogen atom, C1-C25 alkyl, C3-C7 cycloalkyl, C2-C25 alkenyl, C2-C25 cycloalkenyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl or C7-C24 aralkyl;
• R1 and R2 may be connected with each other forming a ring selected from C3-C7 cycloalkyl, C3-C25 cycloalkenyl, C3-C25 cycloalkynyl, C5-C24 aryl, C5-C20 heteroaryl, C5-C24 perhaloaryl, or a 3-12 membered heterocycle, which may be independently substituted with one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perhaloalkyl, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25cycloalkynyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl, C7-C24 aralkyl, C5-C24 perhaloaryl or a 3-12 membered heterocycle;
• L3 is a neutral ligand defined by a general formula 4a, 4b or 4c:
• wherein:
• each of R3 and R4 is independently C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl or C5-C20 heteroaryl, which may be substituted independently with one and/or more substituents selected from the group comprising C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• each of R5, R6, R7, R8, R9, R10 is independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl or C5-C20 heteroaryl, optionally substituted with at least one C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy or a halogen atom, and the R5, R6, R7, R8, R9, R10 groups may optionally interconnect with each other forming a C4-C10 cyclic or a C4-C12 polycyclic system;
• Z is a P(R′)3 group, wherein each R′ can be the same or different and is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl or C3-C12 heteroaryl, and whereby R′ groups may interconnect with each other via carbon atoms forming a 3-12 membered ring;
• or Z may be a neutral ligand;
• or Z may form bidentate and tridentate ligands;
• is a tridentate ligand;
• each of X2 and is independently a bidentate ligand.

A method, comprising:

• activating olefin metathesis ruthenium (pre)catalysts in a metathesis reaction using one of the following compounds;
• copper complexes having at least one organic ligand, or
• ruthenium complexes having at least one organic ligand;
• wherein the copper complexes being the activators of olefin metathesis ruthenium (pre)catalysts have the structure defined by a general formula 1a:
• (CuXaLb)c 1a
• wherein:
• a is 1 or 2;
• b is an integer from 1 to 3;
• c is 1 or 2;
• X is independently an anionic ligand selected from a halogen atom, O(C═O)R′, OR′ or —SR′ group, wherein R′ is a C1-C12 alkyl, a C5-C20 aryl;
• L is independently a neutral ligand selected independently from cyclooctadiene, dicyclopentadiene (DCPD) and a P(R′)3 group, wherein each R′ may be the same or different and is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, C2-C12 alkoxy, C5-C24 aryloxy or C3-C12 heteroaryl, and whereby R′ groups may interconnect with each other via carbon atoms forming a 3-12 membered ring;
• where the neutral L ligands may interconnect with each other, forming bidentate or tridentate ligands;
• or L is a neutral ligand defined by general formulae 4a or 4b:
• wherein:
• each of R3 and R4 is independently C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl or C5-C20 heteroaryl, which may be substituted independently with one and/or more substituents selected from the group comprising C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy or a halogen atom;
• each of R5, R6, R7, R8, R9, R10 is independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl or C5-C20 heteroaryl, optionally substituted with at least one C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy or a halogen atom, and the R5, R6, R7, R8, R9, R10 groups may optionally interconnect with each other forming a C4-C10 cyclic or a C4-C12 polycyclic system;
• wherein the ruthenium complexes being the activators of olefin metathesis ruthenium (pre)catalysts have the structure defined by a general formula 1b:
• (RuX1kX2lL2n)o 1b
• wherein:
• k is an integer from 0 to 2;
• l is 0 or 1;
• m is an integer from 0 to 4;
• n is an integer from 0 to 2;
• o is 1 or 2;
• each of X1 and X2 is independently a halogen atom, —O(C═O)R′ group, wherein R′ is C1-C12 alkyl, C3-C14 cycloalkyl or C5-C14 aryl, and wherein R′ is optionally substituted with at least one C1-C5 alkyl, C3-C6 cycloalkyl, C5-C14 aryl or a halogen atom;
• or each of X1 and X2 is independently an anionic ligand defined by general formulae 6a, 6b and 6c:
• wherein:
• R15 is a hydrogen atom, C1-C12 alkyl, C3-C14 cycloalkyl, C5-C14 aryl, or —O(C═O)R′ group, wherein R′ is C1-C12 alkyl, C3-C14 cycloalkyl or C5-C14 cycloalkyl or C5-C14 aryl, whereby R15 is optionally substituted with at least one C1-C5 alkyl, C3-C6 cycloalkyl, C5-C14 aryl or a halogen atom;
• or X1 and X2 are a bidentate anionic ligand defined by a general formula 7a:
• wherein
• each of R16, R17, R18, R19, R20, R21, R22 is independently a hydrogen atom, C1-C12 alkyl, C3-C14 cycloalkyl, C5-C14 aryl or halogen atom;
• whereby each of R16, R17, R18, R19, R20, R21, R22 is optionally substituted with at least one C1-C5 alkyl, C3-C6 cycloalkyl, C5-C14 aryl or a halogen atom;
• each L1 and L2 is independently a P(R′)3 group, wherein each R′ can be the same or different and is C1-C12 alkyl, C3-C14 cycloalkyl, C5-C14 aryl or C3-C12heteroaryl, and whereby R′ groups may interconnect each other via carbon atoms forming a 3-12 membered ring;
• or L1 and/or L2 are ligands and may connect with each other forming a bidentate ligand defined by general formulae 5a or 5b:
• wherein:
• each of R13 and R14 is independently a hydrogen atom, C1-C12 alkyl or C5-C14 aryl, which may be independently substituted with one and/or more substituents selected from the group comprising C1-C5 alkyl, C3-C6 cycloalkyl or C5-C14 aryl;
• or L2 ligand is a carbene ligand having the structure:
• or each L1 and L2 is independently a neutral ligand selected from benzene and cyclooctadiene.