Carbene precursor compound and use thereof

Patent metadata

Field	Value
Publication number	US-10934320-B2
Application number	US-201916352562-A
Country	US
Kind code	B2
Filing date	Mar 13, 2019
Priority date	Mar 13, 2018
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

Abstract

Provided are a transition metal compound including a novel carbene compound as a ligand, a preparation method thereof, and an application thereof. The transition metal compound according to the present invention may form a structurally stable complex and also have a HOMO-LUMO energy gap and singlet-triplet transition energy which are significantly low as compared with a conventional transition metal compound. In addition, according to the present invention, the transition metal compound may be synthesized in large quantities by a very simple method, thereby having high commercial utility, and thus, an application using the compound is expected.

First claim

What is claimed is:

1. A transition metal compound represented by the following Chemical Formula 1:

wherein
M is a transition metal;
m is an integer of 1 or 2, n is an integer of 0 to 2, and m+n+1 is an oxidation number of a used transition metal;
L 1 is a halogen;
L 2 is carbonyl, nitrile, butadiene, pentadiene, hexadiene, cyclooctadiene, allyl, cyclohexene, cyclooctene, or norbornadiene;
a is an integer of 0 to 4;
R 1 is selected from the group consisting of C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 3 -C 30 cycloalkyl, C 3 -C 30 heterocyclic group, C 6 -C 30 aryl, and C 6 -C 30 heteroaryl;
R 2 is selected from the group consisting of C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C 1 -C 30 alkylamino, halogen, nitro, C 3 -C 30 cycloalkyl, C 3 -C 30 heterocyclic group, C 6 -C 30 aryl, and C 6 -C 30 heteroaryl, and when a is an integer of 2 or more, R 1 is the same or different; and
alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic group, aryl, or heteroaryl of R 1 and alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylamino, cycloalkyl, heterocyclic group, aryl, or heteroaryl of R 2 are independently of one another further substituted by one or more substituents selected from the group consisting of halogen, hydroxy, cyano, C 1 -C 30 alkyl, and haloC 1 -C 30 alkyl, and the heterocyclic group of R 1 or R 2 is of monocyclic or polycyclic non-aromatic ring, and the heteroaryl of R 1 or R 2 is of monocyclic or polycyclic aromatic, wherein the heterocyclic group or the heteroaryl of R 1 or R 2 independently comprises 1 to 9 hetero atoms selected from the group consisting of B, N, O, S, Se, Si and P.

2. The transition metal compound of claim 1 , wherein M is a transition metal of Groups 6 to 11.

3. The transition metal compound of claim 2 , wherein M is a transition metal having an oxidation number of +2 to +4.

4. The transition metal compound of claim 1 , wherein a is an integer of 0 to 2;
R 1 is C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, or C 1 -C 30 alkyl C 6 -C 30 aryl; and
R 2 is C 1 -C 30 alkoxy, C 1 -C 30 alkylamino, halogen, or nitro.

5. The transition metal compound of claim 1 , wherein the transition metal compound is selected from the following structures:

wherein
M′ is a Group 9 transition metal;
M″ is a Group 11 transition metal;
R 11 and R 12 are independently of each other hydrogen, C 1 -C 7 alkoxy, C 1 -C 7 alkylamino, halogen, or nitro; and
R 1 is C 1 -C 7 alkyl, C 3 -C 12 cycloalkyl, or C 1 -C 7 alkyl C 6 -C 12 aryl.

6. A preparation method of a transition metal compound represented by the following Chemical Formula 1, the preparation method comprising a process of reacting a compound of the following Chemical Formula A with a carbonate precursor to prepare a compound of the following Chemical Formula B, and reacting a transition metal precursor in the presence of an organic base:

wherein
M is a transition metal;
m is an integer of 1 or 2, n is an integer of 0 to 2, and m+n+1 is an oxidation number of a used transition metal;
L 1 is a halogen;
L 2 is carbonyl, nitrile, butadiene, pentadiene, hexadiene, cyclooctadiene, allyl, cyclohexene, cyclooctene, or norbornadiene;
X 1 is a halogen;
a is an integer of 0 to 4;
R 1 is selected from the group consisting of C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 3 -C 30 cycloalkyl, C 3 -C 30 heterocyclic group, C 6 -C 30 aryl, and C 6 -C 30 heteroaryl;
R 2 is selected from the group consisting of C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C 1 -C 30 alkylamino, halogen, nitro, C 3 -C 30 cycloalkyl, C 3 -C 30 heterocyclic group, C 6 -C 30 aryl, and C 6 -C 30 heteroaryl, and when a is an integer of 2 or more, R 1 is the same or different; and
alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic group, aryl, or heteroaryl of R 1 and alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylamino, cycloalkyl, heterocyclic group, aryl, or heteroaryl of R 2 are independently of one another further substituted by one or more substituents selected from the group consisting of halogen, hydroxy, cyano, C 1 -C 30 alkyl, and haloC 1 -C 30 alkyl, and the heterocyclic group of R 1 or R 2 is of monocyclic or polycyclic non-aromatic ring, and the heteroaryl of R1 or R2 is of monocyclic or polycyclic aromatic, wherein the heterocyclic group or the heteroaryl of R1 or R2 independently comprises 1 to 9 hetero atoms selected from the group consisting of B, N, O, S, Se, Si and P.

7. The preparation method of claim 6 , wherein the carbonate precursor is selected from the group consisting of phosgene, diphosgene, triphosgene, and bromophosgene.

8. The preparation method of claim 6 , wherein the organic base is selected from the group consisting of lithium hexamethyldisilazide, sodium hexamethyldisilazide, potassium hexamethyldisilazne, and lithium diisopropylamide.

9. The preparation method of claim 6 , wherein the transition metal precursor is selected from the group consisting of Na 2 PdCl 4 , PdCl 2 , Pd(OAc) 2 , RhCl 3 , [Rh(COD)Cl] 2 , IrCl 3 , [Ir(COD)Cl] 2 , Na 2 PtCl 4 , PtCl 2 , and AuCl 3 .

10. The preparation method of claim 6 , further comprising injecting carbon monoxide into a reaction solution, after the process.

Assignees

• Inst Basic Science
• Postech Acad Ind Found

Inventors

• Song Hayoung
• Kim Kimoon
• Lee Eunsung
• Kim Hyunho

Classifications

• B01J2531/822

  Rhodium · CPC title

• C09K2211/185

  of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd · CPC title

• B01J31/1616

  Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00) · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title

• C07F15/0073 Primary

  Rhodium compounds · CPC title