Pincer-type ligand having acridane structure and metal complex using the same

Patent metadata

Field	Value
Publication number	US-11596934-B2
Application number	US-202117165636-A
Country	US
Kind code	B2
Filing date	Feb 2, 2021
Priority date	Jan 30, 2018
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

Disclosed are a pincer-type ligand having a structurally rigid acridane structure and a metal complex consisting of the pincer-type ligand and a metal bound to each other, and exhibiting high reactivity and stability during a variety of bonding activation reactions. T-shaped complexes can be prepared from acri PNP(4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide), which is a pincer-type PNP ligand having an acridane structure, and metal complexes, which can be structurally rigid and thus exhibit excellent reactivity and stability based on minimized structural change thereof, can be prepared by introducing an acridane structure into the backbone thereof. The PNP ligand is structurally stable and has novel chemical properties, as compared to conventional similar ligands, and thus can be utilized in a wide range of catalytic reactions and material chemistry.

First claim

What is claimed is:

1. A metal complex in which the PNP ligand having an acridane structure represented by a following Chemical Formula 1 and a metal are bound to each other:

wherein R, R 1 , R 2 , R 3 and R 4 are each independently hydrogen, a C1 to C20 alkyl group, a halogen-substituted C1 to C20 alkyl group, a C2 to C20 alkenyl group, a halogen-substituted C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a halogen-substituted C1 to C20 alkoxy group, a C3 to C20 cycloalkyl group, a halogen-substituted C3 to C20 cycloalkyl group, a C6 to C40 aryl group, a C5 to C40 heteroaryl group, halogen, C1 to C20 alkylamine, C6 to C40 arylamine, C7 to C60 alkylarylamine, a C1 to C20 thioalkyl group, a C6 to C40 thioaryl group, C1 to C20 alkyl phosphine or C6 to C40 aryl phosphine, with the proviso that when each R is C6 aryl, then R 1 , R 2 , R 3 , and R 4 are not all hydrogen,
wherein the metal is Al, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo.

2. The metal complex of claim 1 , wherein the PNP ligand is represented by a following Chemical Formula 1-1:

3. The metal complex of claim 1 , wherein the metal complex is represented by (PNP)MX n ,
wherein n=0, 1, 2 or 3, and
X is ABC, wherein A, B and C are each independently represented by a monodentate ligand or bidentate ligand.

4. The metal complex of claim 1 , wherein the metal complex is represented by following Chemical Formula 2 or Chemical Formula 3:

wherein M is Al, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo, and X is Cl, Br, OTf, ClO 4 or OAc,

wherein M is Al, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo.

5. The metal complex of claim 1 , wherein the metal complex is selected from the group consisting of Chemical Formulas 2-1 to 2-5 and Chemical Formula 3-1:

6. A method of preparing a metal complex represented by a Chemical Formula 2, comprising:
(a) producing a compound of Chemical Formula 5 by reacting a compound of Chemical Formula 4 with 3 equivalents of alkyl lithium, aryl lithium or a Grignard reagent and 2 equivalents of one compound selected from the group consisting of halogen-substituted alkyl phosphine or aryl phosphine; and
(b) producing a metal complex of Chemical Formula 2 by adding MX n , wherein M is Al, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo, and X is Cl, Br, OTf, ClO 4 or OAc, to the compound of Chemical Formula 5 to induce metallation:

wherein M is Fe, Co, Ni, Co, Pd or Pt, and X is Cl, Br, OTf or OAc.

7. A method of preparing a metal complex represented by a Chemical Formula 3, comprising:
(a) producing a compound of Chemical Formula 5 by reacting a compound of Chemical Formula 4 with 3 equivalents of alkyl lithium, aryl lithium or a Grignard reagent and 2 equivalents of one compound selected from the group consisting halogen-substituted alkyl phosphine or aryl phosphine;
(b) producing a metal complex of Chemical Formula 2 by adding MX2, wherein M is Al, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo, and X is Cl, Br, OTf, ClO 4 or OAc, to the compound of Chemical Formula 5 to induce metallation; and
(c) producing a metal complex of Chemical Formula 3 by adding a reducing agent to the metal complex of Chemical Formula 2,

wherein M is AI, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo, and X is Cl, Br, OTf, ClO 4 or OAc;

wherein M is AI, Cr, Fe, Co, Ti, W, Si, Ir, Rh, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr or Mo.

Assignees

• Korea Advanced Inst Sci & Tech

Inventors

• Lee Yunho
• Yoo Changho
• Choi Jonghoon

Classifications

• C07F15/025

  without a metal-carbon linkage · CPC title

• B01J2531/842

  Iron · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C07F9/5045

  Complexes or chelates of phosphines with metallic compounds or metals · CPC title