# US 2013/0158219 A1 · Supported ligands having a high local density of coordinating atoms

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- Number: US 2013/0158219 A1
- Document ID: US20130158219A1
- Status: Published application
- Kind: A1
- Application number: 13/807,645
- Filed: 2011-06-24
- Published: 2013-06-20
- Earliest claimed: 2010-06-29
- Assignees: Universite De Bourgogne; Centre National De La Recherche Scientifique
- Inventors: Jean-Cyrille Hierso; Matthieu Beauperin; Philippe Meunier
- Web page: https://patentgrep.com/patent/US20130158219A1

## CPC

- C07F 15/02: Iron compounds
- B01J 31/1625: {immobilised by covalent linkages, i.e. pendant complexes with optional linking groups}
- B01J 31/1658: {immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07D 319/06: not condensed with other rings
- C07F 17/02: of metals of Groups 8, 9 or 10 of the Periodic Table
- B01J 2231/4205: C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J 2531/16: Copper
- B01J 2531/824: Palladium
- Y02P 20/50: Improvements relating to the production of bulk chemicals
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention relates to compounds, in particular phosphinic ligands of metal complexes, as well as to metal complexes including said ligands and to supported catalysts including said metal complexes or said compounds. The invention also relates to methods for synthesizing said compounds, to complexes, and to supported catalysts, as well as to intermediate products used in said synthesis methods. The invention further relates to the uses of said compounds. The compounds of the invention are ferrocene compounds which have been functionalized so as to be capable of being heterogenized. The invention can be used in particular in the field of heterogeneous catalysis.

## Claims

### Claim 1

Compounds of formula (I) below:
wherein:
E is a saturated or unsaturated, linear or branched C1 to C30, alkyl chain which optionally contains at least one heteroatom,
GF is vinyl; formyl; carbonyl; acetal; styrenyl; alcohol; silane; alkoxysilane in which the alkoxy chain is a saturated or unsaturated, linear or branched C1 to C30 chain optionally including at least one heteroatom; silanol; siloxane; amine; imine; amide; thiol; or carboxyl, or:
R1 is a phosphine group P(R4)2,
R2 is H or a phosphine group P(R6)2,
X1, X2, X3, and X4 are identical or different and are selected independently of one another from a hydrogen atom, a group P(R8)2, a group —C(CH3)2—P(R3)2, or an amino group R7N(R5)2,
X5 is either a group GF-E-C(CH3)2— in which GF and E are identical to GF and E defined above, or H, or a phosphine group P(R10)2 or an amino group R11N(R9)2,
R3, R4, R5, R6, R7, R8, R9, R10 and R11 are independently a saturated or unsaturated, linear or branched C1 to C30 alkyl group including optionally at least one heteroatom, or a C3 to C7 aryl, or cyclic or acyclic aliphatic group, optionally including a heteroatom, and optionally substituted, with at least one methyl, methoxy, or halogen, or CF3 group.

### Claim 2 (depends on 1)

2) The compounds of claim 1, wherein
X5 is GF-E-C(CH3)2—, and
X1 and X4 are H,
having formula (I-A) below:

### Claim 3 (depends on 1)

3) The compounds of claim 1, wherein X2 and X3 are P(Ph)2, X1 and X4 are H and R1 and R2 are P(Ph)2, and wherein said compounds have the formulae (1) to (8) below, giving a symmetrical compound:

### Claim 4 (depends on 1)

4) The compounds of claim 1, wherein
X5 is different from GF-E-C(CH3)2, making them asymmetrical, and of the formulae (9) to (18) below, in which:
R4 and R6, independently represent an isopropyl, cyclohexyl, tert-butyl, or phenyl, or furyl, group, and are optionally substituted with at least one methyl or methoxy group, a halogen atom or a CF3 group, with R4 and R6 preferably denoting a phenyl group,
R5 denotes:
either a saturated or unsaturated, linear or branched C1 to C30 alkyl chain which may comprise at least one heteroatom,
or a C3 to C7 aryl, or acyclic or cyclic aliphatic, group, optionally comprising a heteroatom and optionally substituted with at least one methyl or methoxy group, a halogen atom, or a CF3 group, with R5 preferably denoting an ethyl group, and wherein said compounds have the formulae (9) to (18) below:

### Claim 5 (depends on 1)

5) Complexes comprising the compounds of claim 1 complexed with a transition metal.

### Claim 6 (depends on 1)

6) Supported complexes comprising the compounds of claim 1 complexed with a transition metal, and immobilized on a support by grafting or polymerizing through the reactive GF group with a reactive group of the support.

### Claim 7 (depends on 1)

7) Supported ligands comprising a compounds of claim 1 immobilized by grafting or polymerizing through its one or more reactive GF groups with one or more reactive groups of a support.

### Claim 8 (depends on 2)

8) A method of synthesizing compounds of claim 2, comprising the steps of:
a) preparing a cyclopentadienyllithium salt carrying the desired groups E and GF or a functional reactive precursor thereof,
b) reacting the compound obtained in step a) in two successive phosphination or lithination reactions, and
c) reacting the compound obtained in step b) with an iron salt to form said compound.

### Claim 9

9) A method of synthesizing a compound of formula (1), comprising the steps of:
a) introducing a functional group GF, comprising a vinyl group —CH═CH2, and a spacer E, which is —CH2—, comprising reacting 6,6-dimethylfulvene with a methyl group the organomagnesium compound CH2═CH—CH2—MgCl, to produce 1-[2-(2-methyl)pent-4-enyl]cyclopentadiene,
b) reacting the product obtained in step a) in a lithiation reaction with n-BuLi, to produce 1-[2-[2-methyl]pent-4-enyl]cyclopentadienyllithium,
c) reacting the product obtained in step b) with ClP(Ph)2 in two successive phosphinations reactions, between which a step of lithiation with n-BuLi is carried out,
d) treating the compound obtained in step c) with n-BuLi, to produce 1,2-bis(diphenylphosphino)-4-[2-(2-methyl)pent-4-enyl]cyclopentadienyllithium, and
e) synthesizing the compound of formula (1) by reacting FeCl2 with the compound obtained in step d).

### Claim 10

10) A method of synthesizing the compound of formula (2), comprising the steps of:
a) reacting an organomagnesium compound of the formula below:
wherein X is Br or I with CH3COCl, to produce 4-(1,3-dioxan-2-yl)butan-2-one of formula A below:
b) reacting the compound of formula A obtained in step a), with pyrrolidine and cyclopentadienyllithium (CpLi), to give the produce 2-[3-(cyclopenta-2,4-dienylidene)butyl]-1,3-dioxane of formula B below:
c) reacting the compound of formula B in a lithiation reaction with methyllithium (MeLi), to produce a compound of formula C below:
d) preforming two successive phosphinations of the compound of formula C with ClP(Ph)2, with intermediate passage to the lithium salt corresponding to the monophosphination by action of n-BuLi, followed by a treatment with n-BuLi, to produce a compound of formula D below:
e) reacting the compound of formula D with an iron salt to produce a compound of formula (2) below:

### Claim 11

11) Compounds comprising one of the following formulae:

### Claim 12

12) A method of synthesizing a compound of formula (3),
comprising deprotecting a compound of formula (2)
under acidic conditions.

### Claim 13

13) A method of synthesizing a supported compound of formula (3),
comprising deprotecting a compound of formula (2)
under acidic conditions and grafting the resulting compound of formula (3) onto a support containing NH2 groups.

### Claim 14

14) A method of synthesizing a compound of formula (4),
comprising reducing a compound of formula (3)

### Claim 15

15) A method of synthesizing a supported compound of formula (4),
comprising grafting a compound of formula (4) with a support comprising reactive groups capable of reacting with an alcohol group, an isocyanate or a silane groups.

### Claim 16

16) A method of synthesizing a compound of formula (5),
comprising reacting a compound of formula (3)
with a compound of formula (I-4):

### Claim 17

17) A method of synthesizing a compound of formula (5),
comprising reacting a compound of formula (3)
with a compound of formula (I-5) below:

### Claim 18

18) A method of synthesizing a compound of formula (6),
comprising reacting a compound of formula (3)
with a p-vinylbenzylamine compound of formula (I-2) below:

### Claim 19

19) A method of synthesizing a supported compound of formula (6),
comprising polymerizing a compound of formula (6) with the styrene compound of formula (I-3):

### Claim 20

20) A method of synthesizing a compound of formula (7),
comprising reacting a compound of formula (4)
with an alkoxysilane compound of formula (I-6):

### Claim 21

21) A method of synthesizing a compound of formula (8),
comprising reacting a compound of formula (3)
with an alkoxysilane compound of formula (I-7):

### Claim 22 (depends on 4)

22) A method of synthesizing a compound having one of formulae (9) to (16) according to claim 4, comprising the steps of:
a) synthesizing a compound of formula D:
b) synthesizing a salt of a metal M, wherein the metal M is a cyclopentadienyl having formula G:
wherein X1, X2, X3, X4, and X5 are as defined in claim 4,
c) reacting the compound obtained in step b) with an iron salt and compound D.

### Claim 23 (depends on 22)

23) A method of synthesizing a compound of formula (9), according to the reaction steps of claim 22, wherein in the compound G, X1, and X4 are H and X2, and X3 are P(Ph)2, and X5 is t-Bu and M is Li.

### Claim 24 (depends on 22)

24) A method of synthesizing a compound of formula (10), according to the reaction steps claim 22, wherein in the compound G, X1, X2, X4, and X5 are H and X3 is P(i-Pr)2 and M is Li.

### Claim 25 (depends on 22)

25) A method of synthesizing a compound of formula (11), according to the reaction steps of claim 22, wherein in compound G, X1, X2, X4, and X5 are H, and X3 is P(R4)2, wherein R4 is a C3 to C7 aryl, cyclic or acyclic aliphatic group, or a saturated or unsaturated, linear or branched C1 to C30, which may comprise at least one heteroatom.

### Claim 26 (depends on 22)

26) A method of synthesizing a compound of formula (12), according to the reaction steps of claim 22, wherein in compound G, M is Li, X1, X2, and X4 are H, X3 is P(R4)2, and X5 is t-Bu, R4 is a C3 to C7 aryl, or cyclic or acyclic aliphatic group, or a saturated or unsaturated, linear or branched C1 to C30 which optionally comprises at least one heteroatom.

### Claim 27 (depends on 22)

27) A method of synthesizing a compound of formula (13), according to the reaction steps of claim 22, wherein in compound G, M is Li, X1, X2, and X4 are H, X3 is P(R4)2, and X5 is P(R6)2 wherein R4 and R6 are, independently a C3 to C7 aryl, or cyclic or acyclic aliphatic, group, or a saturated or unsaturated, linear or branched C1 to C30, which optionally comprises at least one heteroatom.

### Claim 28 (depends on 22)

28) A method of synthesizing a compound of formula (14), according to the reaction steps of claim 22, wherein in compound G, M is Li, X1, X2, X4, and X5 are H, X2 is C(CH3)2—P(R3)2, and R3 is a C3 to C7 aryl, cyclic or acyclic aliphatic group, or a saturated or unsaturated, linear or branched C1 to C30, which optionally comprises at least one heteroatom.

### Claim 29 (depends on 22)

29) A method of synthesizing a compound of formula (15), according to the reaction steps of claim 22, wherein in the compound G, M is Na, X1, X2, X4, and X5 are H, and X3 is CHO.

### Claim 30 (depends on 4)

30) A method of synthesizing a compound of formula (16) according to claim 4, comprising reacting a compound of formula (15) with a secondary amine in the presence of NaBH(OAc)3,
wherein the secondary amine has the formula HN(R5)2
wherein R5 is a C3 to C7 aryl, or cyclic or cyclic aliphatic, group, or a linear or branched C1 to C30 alkyl group which is saturated or unsaturated and may include at least one heteroatom.

### Claim 31 (depends on 4)

31) A method of synthesizing compounds of formulae (17) and (18) according to claim 4, comprising the steps of:
a) synthesizing a compound of formula F:
b) synthesizing a cyclopentadienyl salt of a metal M, having the formula G:
wherein X1, X2, X3, X4, and X5 are as defined above in the compounds of formula (9) to (14), for the asymmetrical tri- or diphosphine compounds of formulae (17) or (18),
c) reaction of the compound obtained in step b) with an iron salt and the compound F.

### Claim 32 (depends on 3, 4)

32) A method of synthesizing metal complexes of formulae (1) to (18) according to claim 3 or 4, comprising complexing each of the compounds of formulae (1) to (18) with a d transition metal.

### Claim 33 (depends on 3, 4, 5)

33) A method of synthesizing metal complexes obtained from the compounds of formulae (1) to (18) according to claim 3 or 4, the comprising grafting or copolymerizing onto a support each of the supported complexes of claim 5.

### Claim 34 (depends on 1)

34) A method of manufacturing a supported catalyst comprising reacting the compounds of claim 1 with a metal.

### Claim 35 (depends on 5)

35) A method of manufacturing a supported catalyst comprising reacting the complexes of claim 5 with a metal.

### Claim 36 (depends on 6)

36) A method for catalytically coupling a nucleophilic and an electrophilic compound, comprising catalyzing the nucleophilic and electrophilic compound in the presence of a catalyst or supported complexes of claim 6.

### Claim 37 (depends on 1)

37) The compounds of claim 1, wherein the C1 to C30 alkyl chain is between C1 to C10.

### Claim 38 (depends on 1)

38) The compounds of claim 1, wherein the C1 to C30 alkyl chain is between C1 to C5.

### Claim 39 (depends on 1)

39) The compounds of claim 1, wherein the heteroatom is N, O, or both.

### Claim 40 (depends on 1)

40) The compounds of claim 1, wherein the alkoxy chain is between C1 to C10.

### Claim 41 (depends on 1)

41) The compounds of claim 1, wherein the alkoxy chain is between C1 to C5.

### Claim 42 (depends on 1)

42) The compounds of claim 1, wherein the halogen is a F or Cl.

### Claim 43 (depends on 1)

43) The compounds of claim 1, wherein R3, R4, R5, R6, R7, R8, R9, R10 and R11 are independently selected from at least one of a methyl, methoxy, halogen, or CF3 group.

### Claim 44 (depends on 1)

44) The compounds of claim 1, wherein R3, R4, R6, R8, and R10 are a phenyl group, R5 and R9 are both an ethyl group, and R7 and R11 are both a —CH2— group.

### Claim 45 (depends on 4)

45) The compounds of claim 4, wherein the halogen atom is F or Cl.

### Claim 46 (depends on 5)

46) The complexes of claim 5, wherein the transition metal is palladium, copper, nickel, platinum, rhodium, iridium, iron, zirconium, titanium, or ruthenium.

### Claim 47 (depends on 5)

47) The complexes of claim 5, wherein the transition metal is palladium.

### Claim 48 (depends on 6)

48) The supported complexes of claim 6, wherein the transition metal is palladium, copper, nickel, platinum, rhodium, iridium, iron, zirconium, titanium, or ruthenium.

### Claim 50 (depends on 6)

50) The supported complexes of claim 6, wherein the transition metal is palladium.

### Claim 51 (depends on 22)

51) The method of claim 22, wherein the salt of metal M is a lithium or sodium salt.

### Claim 52 (depends on 25)

52) The method of claim 25, wherein the saturated or unsaturated, linear or branched C1 to C30 alkyl group is between C3 to C10.

### Claim 53 (depends on 25)

53) The method of claim 25, wherein the C1 to C30 alkyl group is between C3 and C7.

### Claim 54 (depends on 25)

54) The method of claim 25, wherein the heteroatom is N, O, or both.

### Claim 55 (depends on 25)

55) The method of claim 25, wherein R4 is a cyclohexyl, tert-butyl, tert-phenyl, or furyl group that is optionally substituted by a methyl or methoxy group, a halogen atom, or a CF3 group.

### Claim 56 (depends on 55)

56) The method of claim 55, wherein the halogen atom is F, Cl, BR, or I.

### Claim 57 (depends on 55)

57) The method of claim 55, wherein the halogen atom is F or Cl

### Claim 58 (depends on 26)

58) The method of claim 26, wherein the saturated or unsaturated, linear or branched C1 to C30 alkyl group is between C3 to C10.

### Claim 59 (depends on 26)

59) The method of claim 26, wherein the C1 to C30 alkyl group is between C3 and C5.

### Claim 60 (depends on 26)

60) The method of claim 26, wherein the heteroatom is N, O, or both.

### Claim 61 (depends on 26)

61) The method of claim 26, wherein R4 is a isopropyl, cyclohexyl, tert-butyl, phenyl, or furyl group that is optionally substituted by a methyl or methoxy group, a halogen atom, or a CF3 group.

### Claim 62 (depends on 61)

62) The method of claim 61, wherein the halogen atom is F, Cl, BR, or I.

### Claim 63 (depends on 61)

63) The method of claim 61, wherein the halogen atom is F or Cl.

### Claim 64 (depends on 27)

64) The method of claim 27, wherein the saturated or unsaturated, linear or branched C1 to C30 alkyl group is between C3 to C10.

### Claim 65 (depends on 27)

65) The method of claim 27, wherein the C1 to C30 alkyl group is between C3 and C5.

### Claim 66 (depends on 27)

66) The method of claim 27, wherein the heteroatom is N, O, or both.

### Claim 67 (depends on 27)

67) The method of claim 27, wherein R4 and R6 are independently an isopropyl, cyclohexyl, tert-butyl, phenyl, or furyl group that is optionally substituted by a methyl or methoxy group, a halogen atom, or a CF3 group.

### Claim 68 (depends on 67)

68) The method of claim 67, wherein the halogen atom is F, Cl, BR, or I.

### Claim 69 (depends on 67)

69) The method of claim 67, wherein the halogen atom is F or Cl.

### Claim 70 (depends on 28)

70) The method of claim 28, wherein the saturated or unsaturated, linear or branched C1 to C30 alkyl group is between C3 to C10.

### Claim 71 (depends on 28)

71) The method of claim 28, wherein the C1 to C30 alkyl group is between C3 and C5.

### Claim 72 (depends on 28)

72) The method of claim 28, wherein the heteroatom is N, O, or both.

### Claim 73 (depends on 28)

73) The method of claim 28, wherein R3 is an isopropyl, cyclohexyl, tert-butyl, phenyl, or furyl group that is optionally substituted by a methyl or methoxy group, a halogen atom, or a CF3 group.

### Claim 74 (depends on 73)

74) The method of claim 73, wherein the halogen atom is F, Cl, BR, or I.

### Claim 75 (depends on 73)

75) The method of claim 73, wherein the halogen atom is F or Cl.

### Claim 76 (depends on 30)

76) The method of claim 30, wherein the C1 to C30 alkyl group is a C3 to C10 alkyl group.

### Claim 77 (depends on 30)

77) The method of claim 30, wherein the C1 to C30 alkyl group is a C3 to C5 alkyl group.

### Claim 78 (depends on 30)

78) The method of claim 30, wherein the heteroatom is N, O, or both.

### Claim 79 (depends on 30)

79) The method of claim 30, wherein R5 is an ethyl group.

### Claim 80 (depends on 31)

80) The method of claim 31, wherein the salt of metal M is a lithium or sodium salt.

### Claim 81 (depends on 32)

81) The method of claim 32, wherein the d transition metal is palladium, copper, nickel, platinum, iridium, rhodium, iron, zirconium, titanium, or ruthenium.

### Claim 82 (depends on 32)

82) The method of claim 32, wherein the d transition metal is palladium.

### Claim 83 (depends on 3, 4, 32)

83) A method of synthesizing metal complex obtained from the compounds of formulae (1) to (18) as defined by claims 3 and 4 comprising grafting or copolymerizing onto a support the complexes obtained from the process of claim 32.

### Claim 84 (depends on 36)

84) The method of claim 36, wherein the nucleophilic and electrophilic compound is a carbon-carbon, carbon-nitrogen, or carbon-oxygen coupling compound.

### Claim 85 (depends on 33)

85) A method for catalytically coupling a nucleophilic and an electrophilic compound comprising catalyzing the nucleophilic and electrophilic compound in the presence of a metal complex obtained from claim 33.