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US-12624060-B2 - Ruthenium complexes, methods of their preparation and application thereof in olefin cross metathesis

US12624060B2US 12624060 B2US12624060 B2US 12624060B2US-12624060-B2

Abstract

Novel ruthenium complexes of general formula 4 in which the substituents are defined herein. The present disclosure relates also to methods for preparing such compounds and use thereof as catalysts and/or (pre)catalysts in olefin cross metathesis.

Inventors

  • Rafal GAWIN
  • Andrzej Jan TRACZ
  • Patryk KRAJCZY

Assignees

  • APEIRON SYNTHESIS S.A.

Dates

Publication Date
20260512
Application Date
20210817
Priority Date
20200817

Claims (13)

  1. 1 . A compound of general Formula 4 wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 independently of each other denote an entity selected from the group comprising hydrogen atom, alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 7 , alkoxy group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , and halogen atom; wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , and halogen atom, R 18 denotes hydrogen atom, R 19 denotes an entity selected from the group comprising aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aralkyl group C 7 -C 24 , and alkenyl group C 2 -C 6 , wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , halogen atom, —OR′, —CH 2 R′, —CH 2 NR′R″, —SR′, —S(O)R′, —SO 2 R′, —SO 2 NH 2 , —SO 2 NHR′, —SO 2 NR′R″, —NR′R″, —NO 2 , —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, wherein R′ and R″ independently are selected from the group comprising alkyl C 1 -C 6 , cycloalkyl C 3 -C 7 , aryl C 6 -C 24 , heteroaryl C 4 -C 20 , and aralkyl C 7 -C 24 , wherein R′ and R″ are optionally substituted with one or more moieties selected from the group comprising alkyl C 1 -C 12 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently are selected from the group comprising alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , and heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, or R 18 and R 19 are optionally linked to each other thereby forming an aromatic polycyclic system, which may be substituted with one or more substituents selected from group comprising alkyl group C 1 -C 25 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 24 , heteroaryl group C 4 -C 20 , alkenyl group C 2 -C 25 , cycloalkenyl group C 3 -C 25 , alkoxy group C 1 -C 25 , aryloxy group C 6 -C 24 , and heteroaryloxy group C 4 -C 24 , L denotes a neutral ligand, connected with the ruthenium atom via a coordination bond from the heteroatom that forms a part of a compound selected from the group comprising —NR′ 3 , —PR′ 3 , —OR′ 2 , —SR′ 2 , —S(O)R′ 2 , halogen atom, and optionally substituted pyridine (C 5 H 4 NR′), wherein R′ independently is selected from the group comprising hydrogen atom, alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 12 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , aralkyl group C 7 -C 24 , halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, X denotes halogen atom, and n is 1 or 2, wherein L and R 19 are optionally linked to each other.
  2. 2 . The compound of general formula 4 according to claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 are selected from the group comprising hydrogen atom, alkyl group C 1 -C 6 , alkoxy group C 1 -C 6 , halogen atom, and aryl group C 6 -C 10 , R 18 denotes hydrogen atom, R 19 denotes aryl group C 6 -C 10 optionally substituted with at least one alkyl group C 1 -C 6 or —NO 2 , or R 18 and R 19 are optionally linked to each other thereby forming an aromatic polycyclic system, L denotes a neutral ligand selected from the group comprising —NR′ 3 , —PR′ 3 , —OR′ 2 , —SR′ 2 , —S(O)R′ 2 , halogen atom, and optionally substituted pyridine (C 5 H 4 NR′), wherein R′ independently is selected from the group comprising hydrogen atom, alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , or aralkyl group C 7 -C 24 , or halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, and X denote halogen atom, wherein L and R 19 are optionally linked to each other.
  3. 3 . The compound of general formula 4 according to claim 1 , wherein R 3 , R 9 , R 10 , R 15 , R 16 , R 17 and R 18 denote hydrogen atom, R 4 denotes hydrogen atom, alkyl group C 1 -C 6 , or alkoxy group C 1 -C 6 , R 5 denotes hydrogen atom or alkoxy group C 1 -C 6 , R 6 denotes hydrogen atom, alkoxy group C 1 -C 6 or halogen atom, R 7 and R 8 denote hydrogen atom, alkyl group C 1 -C 6 , or aryl group C 6 -C 10 , R 11 and R 12 denote alkyl group C 1 -C 6 , R 13 denotes alkyl group C 1 -C 6 , R 14 denotes alkyl group C 1 -C 6 , R 19 denotes aryl group C 6 -C 10 optionally substituted with at least one alkyl group C 1 -C 6 or —NO 2 , or R 18 and R 19 are optionally linked to each other, forming an aromatic polycyclic system, L denotes a neutral ligand selected from the group comprising —NR′ 3 , —PR′ 3 , —OR′ 2 , —SR′ 2 , —S(O)R′ 2 , halogen atom, and optionally substituted pyridine (C 5 H 4 NR′), wherein R′ independently is selected from the group comprising hydrogen atom, alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , or aralkyl group C 7 -C 24 or halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, X denote halogen atom, and wherein L and R 19 are optionally linked to each other.
  4. 4 . The compound of general formula 4 according to claim 1 , wherein R 3 , R 9 , R 10 , R 15 , R 16 , R 17 and R 18 denote hydrogen atom, R 4 denotes hydrogen atom, methyl group or methoxy group, R 5 denotes hydrogen atom or methoxy group, R 6 denotes hydrogen atom, methoxy group or chlorine atom, R 7 and R 8 denote hydrogen atom, methyl group or phenyl group, R 11 and R 12 denote methyl group, R 13 denotes isopropyl group, R 14 denotes methyl group or isopropyl group, R 19 denotes benzyl group or phenyl group optionally substituted with isopropyl group or nitro group, or R 18 and R 19 together form phenylindenylidene group, L denotes a neutral ligand selected from the group comprising dibenzylamine, benzylmethylamine, isopropyl ether or benzyl ether, iodine atom, triphenylphosphine, dimethylsulfoxide, and pyridine, and X denotes chlorine atom, wherein L and R 19 are optionally linked to each other.
  5. 5 . The compound of general formula 4 according to claim 1 , which is selected from the group comprising the following compounds:
  6. 6 . A method for preparing the compound of general formula 4, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 independently of each other denote an entity selected from the group comprising hydrogen atom, alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 7 , alkoxy group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , and halogen atom; wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , and halogen atom, R 18 denotes hydrogen atom, R 19 denotes an entity selected from the group comprising aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aralkyl group C 7 -C 24 , and alkenyl group C 2 -C 6 , wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , halogen atom, —OR′, —CH 2 R′, —CH 2 NR′R″, —SR′, —S(O)R′, —SO 2 R′, —SO 2 NH 2 , —SO 2 NHR′, —SO 2 NR′R″, —NR′R″, —NO 2 , —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, in which R′ and R″ independently are selected from the group comprising alkyl C 1 -C 6 , cycloalkyl C 3 -C 7 , aryl C 6 -C 24 , heteroaryl C 4 -C 20 , and aralkyl C 7 -C 24 , in which R′ and R″ are optionally substituted with one or more moieties selected from the group comprising alkyl C 1 -C 12 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently are selected from the group comprising alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , and heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, or R 18 and R 19 are optionally linked to each other thereby forming an aromatic polycyclic system, which may be substituted with one or more substituents selected from group comprising alkyl group C 1 -C 25 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 24 , heteroaryl group C 4 -C 20 , alkenyl group C 2 -C 25 , cycloalkenyl group C 3 -C 25 , alkoxy group C 1 -C 25 , aryloxy group C 6 -C 24 , and heteroaryloxy group C 4 -C 24 , L denotes a neutral ligand, connected with the ruthenium atom via a coordination bond from the heteroatom that forms a part of a compound selected from the group comprising —NR′ 3 , —PR′ 3 , —OR′ 2 , —SR′ 2 , —S(O)R′ 2 , halogen atom, and optionally substituted pyridine (C 5 H 4 NR′), in which R′ independently is selected from the group comprising hydrogen atom, alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 12 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , aralkyl group C 7 -C 24 , halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), in which R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, X denotes halogen atom, and n is 1 or 2, wherein L and R 19 are optionally linked to each other, comprising: (1) reacting a salt of general formula 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 independently of each other are an entity selected from the group comprising hydrogen atom, alkyl group C 1 -C 6 , cycloalkyl C 3 -C 7 , alkoxy group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl C 4 -C 20 , and halogen atom; wherein the entity is optionally substituted with at one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , and halogen atom, A-denotes an anion selected from the group comprising halogen anion, BF 4 − , PF 6 − , ClO 4 − , CF 3 SO 2 O − , and HCl 2 − with a base selected from group comprising potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and lithium diisopropylamide; (2) subsequently contacting the reaction product of (1) with a complex of general formula 1 wherein R 18 denotes hydrogen atom, R 19 denotes a compound selected from the group comprising aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aralkyl group C 7 -C 24 , and alkenyl group C 2 -C 6 wherein R 19 optionally is substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , halogen atom, —OR′, —CH 2 R′, —CH 2 NR′R″, —SR′, —S(O)R′, —SO 2 R′, —SO 2 NH 2 , —SO 2 NHR′, —SO 2 NR′R″, —NR′R″, —NO 2 , —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, wherein R′ and R″ independently are selected from the group comprising alkyl C 1 -C 6 , cycloalkyl C 3 -C 7 , aryl C 6 -C 24 , heteroaryl C 4 -C 20 , and aralkyl C 7 -C 24 , wherein R′ and R″ are optionally substituted with one or more moieties selected from the group comprising alkyl C 1 -C 12 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, or R 18 and R 19 are optionally linked to each other, forming an aromatic polycyclic system, which may be substituted with one or more substituents selected from group comprising alkyl group C 1 -C 25 , cycloalkyl group C 3 -C 7 , aryl group C 6 -C 24 , heteroaryl group C 4 -C 20 , alkenyl group C 2 -C 25 , cycloalkenyl group C 3 -C 25 , alkoxy group C 1 -C 25 , aryloxy group C 6 -C 24 and heteroaryloxy group C 4 -C 24 , L denotes a neutral ligand, connected with the ruthenium atom via coordination bond from the heteroatom that forms a part of a compound selected from the group comprising —NR′ 3 , —PR′ 3 , —OR′ 2 , —SR′ 2 , —S(O)R′ 2 , halogen atom, and optionally substituted pyridine (C 5 H 4 NR′), wherein R′ independently is selected from the group comprising hydrogen atom, alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C 1 -C 6 , cycloalkyl group C 3 -C 12 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , aralkyl group C 7 -C 24 , halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other, L′ denotes the neutral ligand P(R′) 3 , wherein each substituent R′ independently is selected from the group comprising alkyl group C 1 -C 12 , cycloalkyl group C 3 -C 12 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 25 , aryloxy group C 6 -C 24 , and heteroaryloxy group C 4 -C 24 , wherein two substituents R′ may be linked to each other thereby forming a heterocycloalkyl ring comprising a phosphorous atom as a ring atom, X denotes halogen atom, wherein L and R 19 are optionally linked to each other; (3) optionally adding a compound of general formula 10 wherein R 20 , R 21 , R 22 , R 23 , R 24 independently are selected from the group comprising hydrogen atom, alkyl group C 1 -C 6 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , alkoxy group C 1 -C 6 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , halogen atom, —CH 2 R′, —SR′, —S(O)R′, —SO 2 R′, —SO 2 NH 2 , —SO 2 NHR′, —SO 2 NR′R″, —NR′R″, —NO 2 , —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, wherein R′ and R″ independently denote alkyl C 1 -C 5 , aryl C 6 -C 24 , wherein R′ and R″ are optionally linked to each other, R 24 denotes hydrogen atom or alkyl group C 1 -C 6 , G denotes halogen atom or substituent selected from group —OR′, —SR′, —NR′R″, —CH 2 NR′R″ wherein R′ and R″ independently denote alkyl group C 1 -C 25 , cycloalkyl group C 3 -C 12 , alkoxy group C 1 -C 25 , aralkyl group C 7 -C 24 , aryl group C 6 -C 20 , heteroaryl group C 4 -C 20 , aryloxy group C 6 -C 24 , heteroaryloxy group C 4 -C 24 , which are optionally substituted with at least one alkyl C 1 -C 12 , alkoxy C 1 -C 12 , aryloxy C 6 -C 24 , heteroaryloxy C 4 -C 24 , halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C 1 -C 12 , cycloalkyl C 3 -C 12 , aryl C 6 -C 20 , heteroaryl C 4 -C 20 , wherein R′ and R″ or R′″ and R″″ are optionally linked to each other; and (4) optionally adding a copper (1) chloride or ArSO 2 Cl, wherein Ar denotes aryl group C 6 -C 20 .
  7. 7 . A method of olefin cross metathesis comprising reacting an olefin with a compound of claim 1 as (pre)catalyst and/or catalyst.
  8. 8 . The method according to claim 7 , wherein the olefin cross metathesis produces at least one compound comprising a terminal double bond C═C as a main product.
  9. 9 . The method according to claim 7 , wherein the olefin contacted during the cross metathesis reaction is ethylene.
  10. 10 . The method according to claim 7 , wherein the compound of claim 1 is used in amount not exceeding 1 ppm.
  11. 11 . The method according to claim 10 , wherein the compound of claim 1 is used in amount from 0.1 to 1 ppm.
  12. 12 . The method according to claim 7 , wherein the cross metathesis reaction is carried out without solvent or is carried out in the presence of an organic solvent selected from group comprising toluene, benzene, mesitylene, dichloromethane, dichloroethane, ethyl acetate, methyl acetate, tert-butyl-methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate, cyclohexane, and mixtures thereof.
  13. 13 . The method according to claim 7 , wherein the cross metathesis reaction is carried out at a temperature within the range of from about 20 to about 150° C., and at a pressure within the range of from about 1 to about 50 bar.

Description

FIELD OF THE INVENTION The present invention, encompassed in the embodiments, relates to novel ruthenium complexes, methods for preparing such compounds and use thereof as catalysts and/or pre-catalysts in olefin cross metathesis, preferably cross-metathesis of olefins involving ethylene. STATE OF THE ART The cross-metathesis involving ethylene as one of the olefins (so-called ethenolysis) is a reaction of great industrial importance. It enables the transformation of olefins containing an internal C═C double bond into compounds with a terminal C═C bond. Among many applications thereof, particular attention should be paid to the possibility of its use in processing of renewable resources such as unsaturated, plant or animal oils and their derivatives. As a result of such processing, compounds with much higher added value are obtained, in particular 1-decene, and esters of 9-decanoic acid (e.g. 9-DAME), which are compounds having high industrial importance, as shown in the reaction below. Cross metathesis reactions involving ethylene typically require the use of catalysts, most often carbene ruthenium complexes. From the industrial point of view, the catalyst for this transformation should be characterized by the following features: a) it should enable the reaction to be carried out efficiently (high conversion) with the least amount of catalyst used (desirable by the industry due to the high cost of the catalyst); b) it should enable the reaction to be carried out in a selective manner in order to produce a minimum amount of side products containing internal C═C bond (formed as a result of secondary metathesis reactions of primary products—terminal olefins, or as a result of homo-metathesis of two substrate molecules). In practice, both aspects may be characterized as the highest possible effective turnover number of the catalyst (TON—turnover number). There are many catalysts for olefin metathesis known in the art (Scheme 2). First generation catalysts (e.g. 1a, 1b) are characterized by good selectivity, but low efficiency in methyl oleate ethenolysis reactions. Second generation catalysts containing NHC carbene ligands with identical aryl substituents on nitrogen atoms (e.g. 2a, 2b) are characterized by both low efficiency and selectivity (Organometallics 2004, 23, 2027-2047; Organometallics 2008, 27, 563-566; Clean 2008, 36, 669-673), the disclosure of which is incorporated by reference herein in its entirety. Less known second generation catalysts containing NHC ligands with mixed aryl and alkyl substituents on nitrogen atoms (e.g. 2c, 2d) offer selectivity and efficiency similar to first generation catalysts (J. Am. Chem. Soc. 2011, 133, 7490-) 7496), the disclosure of which is incorporated by reference herein in its entirety. Low efficiency of the first- and second-generation catalysts containing NHC ligands results from the instability of the propagating methylidene species. Second generation catalysts containing CAAC (cyclic alkyl amino carbene, WO 2006/138166, the disclosure of which is incorporated by reference herein in its entirety) ligand e.g. 3a, 3b, allow higher TON values to be achieved than the TON values achieved using catalysts containing an NHC ligand, due to the much greater stability of the propagating methylidene species, which at the same time provides for high selectivity in ethenolysis reactions (Organometallics 2008, 27, 563-566). There are many second generation ruthenium catalysts containing CAAC ligands substituted in various manners known in the art (Angew. Chem. Int. Ed. 2015, 54, 1919-1923; WO 2015/157736; Angew. Chem. Int. Ed. 2017, 56, 981-986; WO 2017/055945; WO 2019/202509); WO 2010/010290; WO 2017/185324; WO 2011/056881; WO 2020/109217), the disclosures of each of which are incorporated by reference herein in their entirety (Scheme 3, R represents a wide variety of different substituents). Ruthenium catalysts containing CAAC ligands in which R1 and R2 (according to Scheme 3) are alkyl, alkyl substituents substituted with other groups, aryl or aryl substituted with other groups are known in the art. In particular, embodiments where R1 and R2 form a cycloalkyl or heterocycloalkyl system together with the carbon atom to which they are attached also are known. There are no prior art solutions in which the substituents R1 and R2 together with the atom to which they are attached form a different type of cyclic system. There is also an aryl substituent on the nitrogen atom (Ar, according to Scheme 3). Research has focused on the structure-activity relationship of several catalysts in an effort to select the most effective catalyst for ethenolysis (Angew. Chem. Int. Ed. 2015, 54, 1919-1923), the disclosure of which is incorporated by reference herein in its entirety. These studies also made it possible to observe several important effects that shape the current state of the art in the field of catalysts containing CAAC ligands and their applications in ethenolysis reactions. In