Nickel-based complexes and their use in a process for the transformation of olefins

Patent metadata

Field	Value
Publication number	US-9308528-B2
Application number	US-201514694216-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	Apr 28, 2014
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

The invention describes a novel type of nickel-based complex and its preparation method. The invention also concerns the use of said complex in a process for the transformation of olefins.

First claim

The invention claimed is:

1. A nickel-based complex having formula (I)

in which
the atoms P, N, S, O constitute a ligand fragment,
A and A′, which may be identical or different, are independently O, S, NR 3 or a single bond between the phosphorus atom and a carbon atom of R 1a or R 1b ,
the group R 3 is either a hydrogen atom or an alkyl group, which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, or an aromatic group, which may or may not be substituted and which may or may not contain heteroelements,
the groups R 1 , represented in the formula by R 1a and R 1b , with R 1a and R 1b being mutually identical or different and which may or may not be bonded together, are selected from alkyl groups which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, and aromatic groups which may or may not be substituted and which may or may not contain heteroelements,
the group R 2 is selected from alkyl groups which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, and aromatic groups which may or may not be substituted and which may or may not contain heteroelements,
L 1 and L 2 , which may be identical or different, represent a Lewis base,
X 1 is a carbon atom bonded to or forming part of at least one alkyl group, which may or may not be cyclic, which may or may not be unsaturated, which may or may not be substituted and which may or may not contain heteroelements, and an aromatic group which may or may not be substituted and which may or may not contain heteroelements,
L 1 , L 2 and X 1 are such that the oxidation number of the nickel is respected, and δ − represents the delocalisation of the negative charge over the ligand fragment constituted by the atoms P, N, S and O.

2. The complex according to claim 1 , in which L 2 represents a phosphine of the formula P(A 1 R′ 1a )(A′ 1 R′ 1b )(A″ 1 R′ 1c ) or a phosphinamine of the formula (R′ 1a A′ 1 )(R′ 1b A′ 1 )P—NH(R′ 2 ) or (R′ 1a A 1 )(R′ 1b A′ 1 )P—NH—S(O) 2 (R′ 2 ), in which:
A 1 , A′ 1 and A″ 1 , which may be identical or different, are independently O, S, NR 3 or a single bond between the phosphorus atom and a carbon atom of R′ 1a , R′ 1b , or R′ 1c ,
the group R 3 is either a hydrogen atom or an alkyl group, which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, or an aromatic group which may or may not be substituted and which may or may not contain heteroelements,
the groups R′ 1 , i.e. R′ 1a , R′ 1b and R′ 1c , being mutually identical or different and which may or may not be bonded together, are selected from alkyl groups which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, and aromatic groups which may or may not be substituted and which may or may not contain heteroelements,
the group R′ 2 is selected from alkyl groups which may or may not be cyclic, which may or may not be substituted and which may or may not contain heteroelements, and aromatic groups which may or may not be substituted and which may or may not contain heteroelements.

3. The complex according to claim 1 in which, when X 1 is a carbon atom bonded to or forming part of at least one unsaturated, linear or cyclic alkyl group, X 1 and L 1 are bonded in a manner to form an allyl fragment of a linear or cyclic alkyl and permit the formation of a it type nickel-allyl bond.

4. The complex according to claim 1 , in which the groups R 1 , i.e. R 1a and R 1b , which may be identical or different and which may or may not be bonded together, are independently selected from alkyl groups containing 1 to 15 carbon atoms and aromatic groups containing 5 to 20 carbon atoms, which may or may not be substituted and which may or may not contain heteroelements.

5. The complex according to claim 4 , in which the groups R 1 , i.e. R 1a and R 1b , which may be identical or different, which may or may not be bonded together, are independently selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl and adamantyl groups which may or may not be substituted, which may or may not contain heteroelements; and from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-di(trifluoromethyl)phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl and thiophenyl groups, which may or may not be substituted and which may or may not contain heteroelements.

6. The complex according to claim 1 , in which the group R 2 is selected from alkyl groups containing 1 to 15 carbon atoms and aromatic groups containing 5 to 20 carbon atoms, which may or may not be substituted and which may or may not contain heteroelements.

7. The complex according to claim 6 , in which the group R 2 is selected from methyl, trifluoromethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, cyclohexyl and adamantyl groups which may or may not be substituted and which may or may not contain heteroelements; and from phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 3,5-dimethylphenyl, 4-n-butylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl and thiophenyl groups, which may or may not be substituted and which may or may not contain heteroelements.

8. A process for the preparation of a complex according to claim 1 , comprising bringing at least one ligand comprising said ligand fragment constituted by the atoms P, N, S and O into contact with at least one nickel precursor with an oxidation number (0), a precursor of the group X 1 , a precursor of the group L 1 and optionally a precursor of the Lewis base group L 2 .

9. The process according to claim 8 , in which the nickel precursor is selected from nickel(0) bis(cycloocta-1,5-diene), nickel(0) bis(cycloocta-1,3-diene), nickel(0) bis(cyclooctatetraene), nickel(0) bis(cycloocta-1,3,7-triene), bis(o-tolylphosphito)nickel(0) (ethylene), nickel(0) tetrakis (triphenylphosphite), nickel(0) tetrakis(triphenylphosphine) and nickel (0) bis(ethylene), used alone or as a mixture.

10. A process for the preparation of a complex according to claim 1 , comprising bringing at least one ligand comprising said ligand fragment constituted by the atoms P, N, S and O into contact with at least one nickel precursor with an oxidation number (+II), in the presence of a precursor of the group X 1 , a precursor of the group L 1 ′ a reducing agent and optionally a precursor of the Lewis base group L 2 .

11. The process according to claim 10 , in which the nickel precursor is selected from nickel (II) chloride, nickel(dimethoxyethane) chloride(II), nickel(II) bromide, nickel(II)(dimethoxyethane) bromide, nickel(II) fluoride, nickel(II) iodide, nickel(II) sulphate, nickel(II) carbonate, nickel(II) dimethylglyoxime, nickel(II) hydroxide, nickel(II) hydroxyacetate, nickel(II) oxalate, nickel(II) carboxylates such as 2-ethylhexanoate, for example, nickel(II) phenates, nickel(II) acetate, nickel(II) trifluoroacetate, nickel(II) triflate, nickel(II) acetylacetonate, nickel(II) hexafluoroacetylacetonate, allylnickel(II)

Assignees

• IFP Energies Nouvelles
• Univ Amsterdam

Inventors

• Boulens Pierre
• Breuil Pierre-Alain
• Reek Joost
• Olivier-Bourbigou Helene

Classifications

• C07C2531/22

  Organic complexes · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• B01J2540/30

  Non-coordinating groups comprising sulfur · CPC title