SYNTHESIS OF METAL COMPLEXES AND USES THEREOF

• US 20170225157A1
• Filed: 07/24/2015
• Published: 08/10/2017
• Est. Priority Date: 07/25/2014
• Status: Abandoned Application

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: LEE, Han
• Application Number:
  US15/329,027
• Publication Number:
  US 20170225157A1
• Time in Patent Office: Days
• CPC Class Codes: B01J 2231/321 Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
• CPC Class Codes: B01J 2531/0205 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07F 5/069 without C-aluminium linkages

Abstract

The present disclosure provides novel methods of making aluminum complexes with utility for promoting epoxide carbonylation reactions. Methods include reacting neutral metal carbonyl compounds with alkylaluminum complexes.

Claims

1. A method for preparing an aluminum-based carbonylation catalyst of formula:

7. The method of claim 1, wherein the moiety

8. The method of claim 7, wherein the aluminum-porphinato complex has a structure:

9. The method of claim 8, wherein the aluminum-porphinato complex has a structure selected from the group consisting of:

10. The method of claim 7, wherein the aluminum-porphinato complex has the structure:

11. The method of claim 10, wherein the aluminum-porphinato complex has the structure:

12. The method of claim 10, wherein the aluminum-porphinato complex has a structure selected from the group consisting of:

13. The method of claim 1, wherein the neutral metal carbonyl compound is selected from the group consisting of:

Ti(CO)₇, V₂(CO)₁₂, Cr(CO)₆, Mo(CO)₆, W(CO)₆, Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀, Fe(CO)₅, Ru(CO)₅, Os(CO)₅, Ru₃(CO)₁₂, Os₃(CO)₁₂, Fe₃(CO)₁₂, Fe₂(CO)₉, Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, and Ni(CO)₄.

14. The method of claim 1,

wherein the neutral carbonyl compound comprises a cobalt carbonyl compound.

15. The method of claim 14, wherein the cobalt carbonyl compound comprises dicobalt octacarbonyl.

16. The method of claim 1, wherein the composition of catalysts thus formed have halide or alkali metal salts in an amount less than about 200 ppm, less than about 150 ppm, less than about 100 ppm, less than about 50 ppm, less than about 40 ppm, less than about 30 ppm, less than about 20 ppm, less than about 10 ppm, less than about 5 ppm, less than about 2 ppm, or less than about 1 ppm.

2. A method for preparing an aluminum-based carbonylation catalyst of formula:

3. A method for preparing an aluminum-based carbonylation catalyst of formula:

4. A method for preparing an aluminum-based carbonylation catalyst of formula:

5. A method for providing carbonylation catalysts to an epoxide carbonylation reaction,

the epoxide carbonylation reaction comprising a reaction zone where an epoxide is contacted with carbon monoxide,

the method comprising the step of feeding the reaction zone with a first catalyst feed stream containing an aluminum complex of formula I and a second catalyst feed stream containing a neutral metal carbonyl compound,

wherein the aluminum complex of formula I has a formula:

6. A method of synthesizing a symmetrical ketone comprising the step of contacting an aluminum compound of formula I: