Synthesis of open metal carbonyl clusters

Patent metadata

Field	Value
Publication number	US-9266915-B2
Application number	US-201514731082-A
Country	US
Kind code	B2
Filing date	Jun 4, 2015
Priority date	Sep 24, 2012
Publication date	Feb 23, 2016
Grant date	Feb 23, 2016

Abstract

The present invention is directed to the synthesis of novel stable open metal clusters by selective oxidation of bound ligands. The synthesis comprises, for example, using an amine based oxidant for decarbonylation of specific carbonyl ligands. The synthesis can also comprise further removal of a bound amine group by an acid. The resulting metal cluster contains a coordinatively unsaturated site comprising a carbonyl vacancy. The resulting metal cluster can be used as a catalyst in a variety of chemical transformations.

First claim

We claim:

1. A method for preparing an open metal carbonyl cluster comprising chemically reacting a closed metal carbonyl cluster and an opening agent, with the opening agent reacting with a bound carbonyl group so as to unbind it from the cluster and leave behind a CO-labile ligand on the cluster, and wherein the closed metal carbonyl cluster is bound with three sterically protective ligands.

2. The method of claim 1 , wherein the ligands are calixarene phosphine ligands.

3. The method of claim 1 , wherein the closed metal carbonyl cluster is an Ir 4 carbonyl cluster bound with three calixarene phosphine ligands, and the opening agent is trimethylamine oxide.

4. The method of claim 1 , further comprising recovering the open metal carbonyl cluster, supporting the cluster on a catalyst support, and treating the supported cluster via an oxidation reaction by exposure to oxygen.

5. An open metal carbonyl cluster prepared by the method of claim 1 , which is supported on a catalyst support.

6. The open metal carbonyl cluster of claim 5 , wherein the catalyst support comprises silica and/or alumina, carbon, magnesia, or ceria.

7. A chemical catalytic reaction comprising conducting a chemical reaction in the presence of the open metal carbonyl cluster prepared in claim 1 .

8. A chemical catalytic reaction comprising conducting a chemical reaction in the presence of the supported and treated open metal carbonyl cluster prepared in claim 4 .

9. A method for preparing an open metal carbonyl cluster comprising chemically reacting a closed metal carbonyl cluster and an opening agent, with the opening agent reacting with a bound carbonyl group so as to unbind it from the cluster and leave behind a CO-labile ligand on the cluster, and then removing the CO-labile ligand to create vacant sites, wherein the co-labile ligand is removed by reaction with a strong acid or by heating the open metal carbonyl cluster under flow of an inert gas.

10. The method of claim 9 , wherein the CO-labile ligand is removed by reaction with a strong acid.

11. The method of claim 10 , wherein the strong acid is triflic acid.

12. The method of claim 9 , wherein the CO-labile ligand is removed to create vacant sites by heating the open metal carbonyl cluster under flow of an inert gas.

13. The method of claim 9 , wherein the CO-labile ligand comprises a trimethylamine oxide ligand.

14. The method of claim 9 , wherein the CO-labile ligand is a nitrogen-containing compound coordinating through nitrogen or an oxygen-containing compound coordinating through oxygen.

15. The method of claim 9 , wherein the CO-labile ligand is an ether, amine, dioxygen or nitrogen.

16. The method of claim 9 , further comprising recovering the open metal carbonyl cluster, supporting the cluster on a catalyst support, and treating the supported cluster via an oxidation reaction by exposure to oxygen.

17. An open metal carbonyl cluster prepared by the method of claim 9 , which is supported on a catalyst support.

18. The open metal carbonyl cluster in claim 17 , wherein the catalyst support comprises silica and/or alumina, carbon, magnesia, or ceria.

19. A chemical catalytic reaction comprising conducting a chemical reaction in the presence of the open metal carbonyl cluster prepared in claim 9 .

20. A chemical catalytic reaction comprising conducting a chemical reaction in the presence of the supported and treated open metal carbonyl cluster prepared in claim 16 .

21. The method of claim 9 , wherein the closed metal carbonyl cluster is bound with three sterically protective ligands.

22. The method of claim 21 , wherein the ligands are calixarene phosphine ligands.

Assignees

• Chevron Usa Inc
• Univ California

Inventors

• Katz Alexander S
• Kuperman Alexander
• Okrut Alexander
• Runnebaum Ron C
• Ouyang Xiaoying

Classifications

• C07F15/004 Primary

  without a metal-carbon linkage · CPC title

• B01J37/12

  Oxidising · CPC title

• B01J31/1683

  the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes · CPC title

• B01J2531/0288

  Sterically demanding or shielding ligands · CPC title

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title