US 12,338,310 B2
Use of metal complexes having organic ligands for activating olefin metathesis ruthenium (pre)catalysts
Michal Chwalba, Wroclaw (PL); Konrad Kurcbach, Brzeziny (PL); Krzysztof Greda, Wroclaw (PL); Rafal Gawin, Warsaw (PL); and Krzysztof Skowerski, Jablonowo Pomorskie (PL)
Assigned to APEIRON SYNTHESIS SPOLKA AKCYJNA, Wroclaw (PL)
Appl. No. 17/600,832
Filed by APEIRON SYNTHESIS SPOLKA AKCYJNA, Wroclaw (PL)
PCT Filed Mar. 31, 2020, PCT No. PCT/EP2020/059181
§ 371(c)(1), (2) Date Oct. 1, 2021,
PCT Pub. No. WO2020/201314, PCT Pub. Date Oct. 8, 2020.
Claims priority of application No. 429476 (PL), filed on Apr. 2, 2019.
Prior Publication US 2022/0177612 A1, Jun. 9, 2022
Int. Cl. C08F 4/50 (2006.01); C08F 2/06 (2006.01); C08F 10/00 (2006.01)
CPC C08F 4/50 (2013.01) [C08F 2/06 (2013.01); C08F 10/00 (2013.01); B01J 2231/54 (2013.01); B01J 2531/16 (2013.01); B01J 2531/821 (2013.01); C08G 2261/418 (2013.01)] 18 Claims
 
1. 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 described 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 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 a C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl or 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 denotes C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, C2-C12 alkoxy, C5-C24 aryloxy or C3-C12 heteroaryl, and R′ groups may interconnect with each other via carbon atoms forming a 3-12 membered ring;
whereby the neutral L ligands may interconnect with each other, forming bidentate or tridentate ligands;
or L is a neutral ligand defined by a general formula 4a, 4b or 4c:

OG Complex Work Unit Chemistry
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 activators of olefin metathesis ruthenium (pre)catalysts have a structure described by a general formula 1b:
(RuX1kX2jL1mL2n)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 the number 1 or 2;
each of X1 and X2 is independently a halogen atom, or —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;
each of L1 and L2 is independently a P(R′)3 group, wherein each R′ may be the same or different and is C1-C12 alkyl, C3-C14 cycloalkyl, C5-C14 aryl or C3-C12 heteroaryl, and R′ groups may interconnect with 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:

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wherein:
p is the number 1 or 2;
each of R13 and R14 is independently a hydrogen atom, C1-C12 alkyl, C3-C14 cycloalkyl or C5-C14 aryl, optionally substituted with at least one C1-C5 alkyl, C3-C6 cycloalkyl, C5-C14 aryl or halogen atom;
or L2 ligand is a carbene ligand of the structure:

OG Complex Work Unit Chemistry
or each of L1 and L2 is independently a neutral ligand selected from benzene, p-cymene, mesitylene and cyclooctadiene.