Metal complexes

Patent metadata

Field	Value
Publication number	US-10717754-B2
Application number	US-201616063049-A
Country	US
Kind code	B2
Filing date	Dec 19, 2016
Priority date	Dec 18, 2015
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

Metal complexes such as those of formula (I) are contemplated by the present invention. The metal complexes may be used in catalytic reactions as a catalyst. The catalytic reaction may be an autotransfer process, for example hydrogen borrowing. Improved catalytic activity has been observed with certain metal complexes of the invention.

First claim

The invention claimed is:

1. A metal complex of formula (I)

wherein
M is iridium;
L 1 and L 2 are independently selected from: a halogen, a nitrile, an amine, a phosphine, a phosphite, a sulfonate ester, a N-heterocyclic carbene or a 5 or 6 membered heterocyclic ring or L 1 and L 2 taken together are a bidentate ligand selected from: a diamine, a diphosphine, a diphosphite, a disulfonate ester, an amino acid or derivative thereof, an amino alcohol, aminosulfonamides, an N-heterocyclic carbene, a diketonate and substituted or unsubstituted bipyridine,
wherein L 1 and L 2 groups are unsubstituted or optionally substituted by halo, C 1-4 alkyl, C 1-4 haloalkyl, —OR A , —NR A R B , —CN, —SO 2 R A ;
R 1 is H;
R 2 is represented by H, substituted or unsubstituted: C 1-14 alkyl, C 1-14 haloalkyl, a C 3-8 carbocyclic ring, or a 3 to 8 membered heterocyclic ring, or a C 1-14 alkyl substituted with phenyl, a fluorous tag, or a solid support;
R 3 and R 4 are each independently selected from: H, halo, C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, phenyl, a 5 or 6 membered heteroaryl ring and —OR A1 ;
or R 3 and R 4 along with the shared, adjacent or non-adjacent carbon atoms to which they are attached together form a 3 to 8 membered carbocyclic ring,

or R 2 and one of R 3 and R 4 , together with the atoms to which they are attached, form a 3 to 8 membered heterocyclic ring;
R 5 is selected from halo, C 1-6 alkyl, C 1-6 haloalkyl and C 3-6 cycloalkyl, C 6 aryl or 5 or 6 membered heteroaryl
or two adjacent R 5 groups, together with the atoms to which they are attached, form a 5 or 6 membered carbocyclic ring;

p is 0 or 1 or more;
n is selected from 1 to 10;
m is selected from 0, 1, 2, 3 or 4; and
R A , R B and R A1 are at each occurrence independently selected from: H, C 1-6 alkyl or C 1-6 haloalkyl.

2. The metal complex of claim 1 , wherein R 3 and R 4 are each independently selected from: H, halo, C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, phenyl, or a 5 or 6 membered heteroaryl ring and —OR A1 ;
or R 3 and R 4 along with the shared, adjacent or non-adjacent carbon atoms to which they are attached together form a 5 or 6 membered carbocyclic ring.

3. The metal complex of claim 1 , wherein p is 0.

4. The metal complex of claim 1 , wherein R 5 is C 1-6 alkyl.

5. The metal complex of claim 1 , wherein m is 0 or 4.

6. The metal complex of claim 1 wherein
L 1 and L 2 are independently is a halogen, a nitrile, an amine, a phosphine or a 5 or 6 membered heterocyclic ring or
L 1 and L 2 taken together are a bidentate ligand selected from the group consisting of a diamine, a diphosphine, and substituted or unsubstituted bipyridine,
wherein L 1 and L 2 groups are unsubstituted or optionally substituted by halo, C 1-4 alkyl, C 1-4 haloalkyl, —OR A , —NR A R B , —CN, or —SO 2 R A .

7. The metal complex of claim 1 wherein L 1 and L 2 are independently halo, C 1-10 alkylnitriles, or a 5 or 6 membered heteroaryl ring or
L 1 and L 2 taken together are bipyridine or C 1-10 alkyldiphosphine.

8. The metal complex of claim 1 , wherein R 2 is independently H, methyl, ethyl, phenyl, benzyl, iso-propyl, tert-butyl, a fluorous tag, a solid support or R 2 and one of R 3 and R 4 together with the atoms to which they are attached form a 5 or 6 membered heterocyclic ring.

9. The metal complex of claim 1 wherein n is 2, 3 or 4.

10. A catalytic hydrogen autotransfer process comprising adding the metal complex of claim 1 to a reaction mixture.

11. A metal complex may be a compound according to formula (II):

wherein X is 1, 2 or 3 anion molecules
and
M is iridium;
L 1 and L 2 are independently selected from: a halogen, a nitrile, an amine, a phosphine, a phosphite, a sulfonate ester, a N-heterocyclic carbene or a 5 or 6 membered heterocyclic ring or L 1 and L 2 taken together are a bidentate ligand selected from: a diamine, a diphosphine, a diphosphite, a disulfonate ester, an amino acid or derivative thereof, an amino alcohol, aminosulfonamides, an N-heterocyclic carbene, a diketonate and substituted or unsubstituted bipyridine,
wherein L 1 and L 2 groups are unsubstituted or optionally substituted by halo, C 1-4 alkyl, C 1-4 haloalkyl, —OR A , —NR A R B , —CN, —SO 2 R A ;
R 1 is H
R 2 is represented by H, substituted or unsubstituted: C 1-14 alkyl, C 1-14 haloalkyl, C 3-8 carbocyclic ring, or a 3 to 8 membered heterocyclic ring, or a C 1-14 alkyl substituted with phenyl, a fluorous tag, or a solid support;
R 3 and R 4 are each independently selected from: H, halo, C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, phenyl, a 5 or 6 membered heteroaryl ring and —OR A1 ;
or R 3 and R 4 along with the shared, adjacent or non-adjacent carbon atoms to which they are attached together form a 3 to 8 membered carbocyclic ring,

or R 2 and one of R 3 and R 4 , together with the atoms to which they are attached, form a 3 to 8 membered heterocyclic ring;
R 5 is selected from halo, C 1-6 alkyl, C 1-6 haloalkyl and C 3-6 cycloalkyl, C 6 aryl or 5 or 6 membered heteroaryl
or two adjacent R groups, together with the atoms to which they are attached, form a 5 or 6 membered carbocyclic ring;

p is 1 or more;
n is selected from 1 to 10;
m is selected from 0, 1, 2, 3 or 4; and
R A , R B and R A1 are at each occurrence independently selected from: H, C 1-6 alkyl or C 1-6 haloalkyl.

12. The metal complex of claim 11 , wherein R 3 and R 4 are each independently selected from: H, halo, C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, phenyl, or a 5 or 6 membered heteroaryl ring and —OR A1 ;
or R 3 and R 4 along with the shared, adjacent or non-adjacent carbon atoms to which they are attached together form a 5 or 6 membered carbocyclic ring.

13. The metal complex of claim 11 , wherein X is a monoanionic, dianionic or trianionic molecule.

14. The metal complex of claim 11 , wherein p is 2.

15. The metal complex of claim 11 , wherein X is a hydroxide, fluoride, chloride, bromide, iodide, acetate, formate, fluorate, fluorite, bromate, bromite, iodate, iodite, chlorate, chlorite, hydrogen carbonate, hypofluorite, hypochlorite, hypobromite, hypoiodite, perfluorate, perchlorate, perbromate, periodate, chromate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, nitrate, hydrogen oxalate, hydrogen sulfate, hydrogen sulfite, permanganate, nitrite, thiocyanate, hydride, hexafluorophosphate, hexafluoroantiminate, tetrafluoroborate, peroxide, [B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ] − , B(C 6 F 5 ) 4 − , Al(OC(CF 3 ) 3 ) 4 − , sulfate, sulfite, sulfide, persulfate, thiosulfate, hyposulfite, hydrogen phosphate, hydrogen phosphite, metasilicate, carbonate, percarbonate, oxalate, benzoate, tartrate, borate, boride, citrate, hypophosphite, nitride, phosphate, phosphide, or phosphite.

16. A metal complex of claim 11 , wherein the compound is

17. A metal complex wherein the complex is

Assignees

• Univ Leeds Innovations Ltd

Inventors

• Marsden Stephen Philip
• Mcgowan Patrick Columba
• Lanaro Roberta
• Blacker Andrew John

Classifications

• C07F17/02 Primary

  of metals of Groups 8, 9 or 10 of the Periodic Table · CPC title

• C07D295/03

  with the ring nitrogen atoms directly attached to acyclic carbon atoms · CPC title

• C07D295/023

  Preparation; Separation; Stabilisation; Use of additives · CPC title

• B01J2531/827

  Iridium · CPC title

• B01J2531/822

  Rhodium · CPC title