Heterogeneous catalysts for nmr/mri enhancement via signal amplification by reversible exchange (sabre)

Patent metadata

Field	Value
Publication number	US-2016016159-A1
Application number	US-201514801541-A
Country	US
Kind code	A1
Filing date	Jul 16, 2015
Priority date	Jul 17, 2014
Publication date	Jan 21, 2016
Grant date	—

Abstract

Heterogeneous iridium catalysts for nuclear spin polarization enhancement in solution via signal amplification by reversible exchange are provided. Also provided are methods for preparing heterogeneous iridium catalysts, and methods of using heterogeneous iridium catalysts for nuclear spin polarization enhancement in solution via signal amplification by reversible exchange.

First claim

What is claimed is:

1 . A heterogeneous catalyst of formula (I),

wherein,

is a solid support;
L is a bond or a linker; and
Cat has formula:

wherein R 1 and R 2 are each independently selected from aryl, heteroaryl, arylalkyl, heteroarylalkyl, wherein said aryl, heteroaryl, arylalkyl, and heteroarylalkyl are each independently unsubstituted or substituted with one or more suitable substituents; R 3 and R 4 are each independently selected from hydrogen and alkyl; R 5 is halogen or pyridinyl, wherein said pyridinyl is unsubstituted or substituted with one or more suitable substituents; provided that one R 1 , R 2 , R 3 , R 4 , and R 5 links to the solid support via L.

2 . The catalyst of claim 1 , wherein formula (II) has formula:

where X − is a non-coordinating anion.

3 . The catalyst of claim 1 , wherein formula (II) has formula:

4 . The catalyst of claim 1 , wherein the solid support is selected from a nanoparticle, a titanium dioxide nanoparticle, silica, a polymer microbead, and a polystyrene microbead.

5 . The catalyst of claim 1 , wherein L is a bond.

6 . The catalyst of claim 1 , wherein L is a linker, wherein the linker is derived from an amino acid or 4-dimethylamino-pyridine.

7 . The catalyst of claim 1 , wherein R 1 is mesityl.

8 . The catalyst of claim 1 , wherein R 2 is mesityl.

9 . The catalyst of claim 1 , wherein R 3 and R 4 are each hydrogen.

10 . The catalyst of claim 1 , wherein R 5 is chloro.

11 . The catalyst of claim 1 , wherein R 5 is an unsubstituted or substituted pyridinyl.

12 . The catalyst of claim 1 , having formula (I-a),

wherein Mes is mesityl; and X − is a non-coordinating anion.

13 . The catalyst of claim 1 , having formula (I-b),

wherein Mes is mesityl; and X − is a non-coordinating anion.

14 . The catalyst of claim 1 , having formula (I-c),

wherein Mes is mesityl; and X − is a non-coordinating anion.

15 . The catalyst of claim 14 , wherein the solid support is a TiO 2 nanoparticle.

16 . The catalyst of claim 1 , having formula (I-d),

wherein Mes is mesityl; X − is a non-coordinating anion; and the solid support is polystyrene.

17 . The catalyst of claim 1 , having formula (I-e),

wherein Mes is mesityl; and X − is a non-coordinating anion.

18 . The catalyst of claim 1 , having formula (I-f),

wherein Mes is mesityl; X − is a non-coordinating anion; and the solid support is a TiO 2 nanoparticle.

Assignees

• Univ Vanderbilt
• Univ Southern Illinois

Inventors

• Goodson Boyd M
• Chekmenev Eduard Y
• Shi Fan
• Coffey Aaron M

Classifications

• 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

• B01J31/1658

  immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J2531/827

  Iridium · CPC title

• B01J31/2295 Primary

  Cyclic compounds, e.g. cyclopentadienyls · CPC title