Dihydroxybipyridine complexes of ruthenium and iridium for water oxidation and hydrogenation

Patent metadata

Field	Value
Publication number	US-9527066-B2
Application number	US-201214342077-A
Country	US
Kind code	B2
Filing date	Aug 27, 2012
Priority date	Aug 30, 2011
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

The present invention discloses a class of organometallic catalysts for both hydrogenation and water oxidation. The synthesis and the use of these catalysts for hydrogenation, hydrogen production and water oxidation reactions is also disclosed.

First claim

What is claimed is:

1. An organometallic complex represented by the formula:

wherein Y is selected from the group consisting of F − , Cl − , Br − , I − , alkoxy groups, PF 6 − , BF 4 − , B(ArF) 4 − , ClO 4 − , SbF 6 − , SO 4 2− , trifluoroacetate, and thiocynanates.

2. The organometallic complex of claim 1 , wherein Y is selected from the group consisting of F − , Cl − , Br − and I − .

3. A method for the production of an organometallic complex represented by the formula:

wherein Y is selected from the group consisting of F − , Cl − , Br − , I − , alkoxy groups, PF 6 − , BF 4 − , B(ArF) 4 − , ClO 4 − , SbF 6 − , SO 4 2− , trifluoroacetate, and thiocyanates;
starting from a bipyridinone represented by formula:

said method comprising the steps of allowing said bipyridinone to tautomerize to produce 6,6′-Dihydroxybipyridine; and reacting said 6,6′-dihydroxybipyridine with a ruthenium metal complex.

4. The method of claim 3 , wherein said ruthenium metal complex is [(p-cymene)RuCl 2 ] 2 .

5. A method of using an organometallic complex represented by the formula:

wherein Y is selected from the group consisting of F − , Cl − , Br − , I − , alkoxy groups, PF 6 − , BF 4 − , B(ArF) 4 − , ClO 4 − , SbF 6 − , SO 4 2− , trifluoroacetate, and thiocyanates, comprising step of contacting a substrate with a source of hydrogen in the presence of said organometallic complex under conditions suitable to hydrogenate or reduce said substrate.

6. The method of claim 5 , wherein said hydrogenation is carried out in an aqueous solution.

7. The method of claim 5 , wherein said substrate is CO 2 , a ketone, or an amine and the reaction is carried out in the presence of a base.

8. A method of using an organometallic complex represented by the formula:

wherein Y is selected from the group consisting of F − , Cl − , Br − , I − , alkoxy groups, PF 6 − , BF 4 − , B(ArF) 4 − , ClO 4 − , SbF 6 − , SO 4 2− , trifluoroacetate, and thiocyanates, comprising step of contacting an oxidizing agent with water in the presence of said organometallic complex under conditions suitable for water oxidation.

9. The method of claim 8 , wherein said oxidizing agent is selected from the group consisting of an oxidation agent containing metals in a high oxidation state, an oxidizing agent containing non metal in a high oxidation state, sodium periodate, persulfate, cobalt (III) complexes, and ruthenium (III) complexes.

10. The method of claim 8 , wherein the water oxidation is driven, at least partially, by sunlight or electricity.

11. The method of claim 8 , where said oxidization is carried out in sunlight.

12. A method of using an organometallic complex represented by the formula:

wherein Y is selected from the group consisting of F − , Cl − , Br − , I − , alkoxy groups, PF 6 − , BF 4 − , B(ArF) 4 − , ClO 4 − , SbF 6 − , SO 4 2− , trifluoroacetate, and thiocyanates, comprising step of contacting water with an oxidizing agent in the presence of said organometallic complex under conditions suitable to oxidize said water.

Assignees

• Papish Elizabeth T
• Nieto Ismael
• Univ Alabama

Inventors

• Papish Elizabeth T
• Nieto Ismael

Classifications

• C07F15/0033 Primary

  Iridium compounds · CPC title

• B01J31/181

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine · CPC title

• C01B3/06

  by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents · CPC title

• B01J2531/827

  Iridium · CPC title

• B01J31/1815

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title