Hydroxylation of icosahedral boron compounds

• US 8,741,250 B2
• Filed: 08/03/2012
• Issued: 06/03/2014
• Est. Priority Date: 08/05/2011
• Status: Active Grant

• Current Assignee: Curators of the University of Missouri (University of Missouri)
• Original Assignee: Curators of the University of Missouri (University of Missouri)
• Inventors: Hawthorne, M. Frederick, Bondarev, Oleg
• Primary Examiner(s): Zimmer, Anthony J
• Assistant Examiner(s): BOVA, JUSTIN M
• Application Number:
  US13/566,789
• Publication Number:
  US 20130078175A1
• Time in Patent Office: 669 Days
• Field of Search: 423/276, 423/277, 568/4, 568/5
• US Class Current: 423/277
• CPC Class Codes: C01B 35/10 Compounds containing boron and oxygen C01B35/06 takes precedence
• CPC Class Codes: C01B 35/14 Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
• CPC Class Codes: C07F 5/02 Boron compounds

Abstract

The present invention relates to a synthetic method for producing a per-hydroxylated icosahedral boron compound via catalytic hydroxylation of icosahedral boron compound using a soft electrophile.

Claims

1. A method of producing a per-hydroxylated icosahedral boron compound, the method comprising the steps of:

(a) contacting an icosahedral boron compound with a soft electrophile and a sulfonic acid such that a sulfonated intermediate is formed; and

(b) hydrolyzing the sulfonated intermediate to give the per-hydroxylated icosahedral boron compound.

2. The method of claim 1, wherein the icosahedral boron compound comprises [closo-B₁₂H₁₂]²⁻

and the per-hydroxylated boron compound comprises [closo-B₁₂(OH)₁₂]²⁻

.

3. The method of claim 2, wherein the soft electrophile is a platinum species, a palladium species, or an iodine species.

4. The method of claim 2, wherein the soft electrophile is Pt(bpym)Cl₂.

5. The method of claim 2, wherein the soft electrophile is Pt(NH₃)₂Cl₂.

6. The method of claim 2, wherein the soft electrophile is PdCl₂.

7. The method of claim 2, wherein the soft electrophile is iodine cation.

8. The method of claim 2, wherein the soft electrophile is added in an amount ranging from about 0.5 mol % to about 5 mol % to the [closo-B₁₂H₁₂]²⁻

.

9. The method of claim 2, wherein step (a) is conducted at a temperature ranging from about 160°

C. to about 200°

C.

10. The method of claim 2, wherein step (a) is conducted over a period of about 18 hours.

11. The method of claim 2, wherein step (b) comprises an acid hydrolysis.

12. The method of claim 2, wherein step (b) comprises addition of water.

13. The method of claim 2, the method further comprising formation of an alkali boron by contacting the compound comprising [closo-B₁₂(OH)₁₂]²⁻

with an alkali carbonate or alkanol.

14. The method of claim 2, wherein step (a) is conducted in the absence of hydrogen peroxide or a reactive oxygen species.

15. The method of claim 2, wherein the reaction is conducted in one pot.

16. A composition comprising [closo-B₁₂(OSO₃R¹)₁₂]²⁻

, wherein R¹ is hydrocarbyl, substituted hydrocarbyl, hydrogen, or is not present such that the sulfonated intermediate is anionic.

17. The composition of claim 16, wherein R¹ is hydrogen.

18. A method of producing a compound comprising [closo-B₁₂(OH)₁₂]²⁻

, the method comprising the steps of;

(a) contacting a compound comprising [closo-B₁₂H₁₂]²⁻

with about 0.5 mol % to about 5 mol % of a soft electrophile selected from a group consisting of a palladium species, a platinum species, and an iodine species, and with sulfuric acid such that a sulfonated intermediate is formed; and

(b) hydrolyzing the sulfonated intermediate to give the compound comprising [closo-B₁₂(OH)₁₂]²⁻

.

19. The method of claim 18, wherein the platinum species is Pt(bpym)Cl₂.

20. The method of claim 18, wherein the platinum species is Pt(NH₃)₂Cl₂.

21. The method of claim 18, wherein the palladium species is PdCl₂.

22. The method of claim 18, wherein the iodine species is iodine cation.

23. The method of claim 18, wherein step (a) is conducted at a temperature ranging from about 160°

C. to about 200°

C.

24. The method of claim 18, wherein step (b) comprises an acid hydrolysis.

25. The method of claim 18, wherein step (b) comprises addition of water.