Complex and use of same

Patent metadata

Field	Value
Publication number	US-9890184-B2
Application number	US-201314443888-A
Country	US
Kind code	B2
Filing date	Nov 20, 2013
Priority date	Nov 20, 2012
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

A novel complex capable of fixing dinitrogen and use thereof are provided. A complex represented by formula (1A) or (1B) or a cationic or anionic complex from the complex:

wherein M1 to M4 (M1 to M3 in the case of formula (1A)) are each independently Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W, and L1 to L4 (L1 to L3 in the case of formula (1A)) are each independently a ligand selected from among a ligand (Cp) including a substituted or unsubstituted cyclopentadienyl derivative, a diphenylamine ligand, a diphenylphosphine ligand, and a carboimideamide ligand.

First claim

The invention claimed is:

1. A complex represented by formula (1A) or (1B) or a cationic or anionic complex from the complex:

wherein M1 to M4 (M1 to M3 in the case of formula (1A)) are each independently Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W, and L1 to L4 (L1 to L3 in the case of formula (1A)) are each independently a ligand selected from the group consisting of a ligand (Cp) including a substituted or unsubstituted cyclopentadienyl derivative, a diphenylamine ligand, a diphenylphosphine ligand, and a carboimideamide ligand.

2. The complex as set forth in claim 1 , wherein L1 to L4 (L1 to L3 in the case of formula (1A)) of formulas (1A) and (1B) are identical ligands each of which is represented by formula (2):

wherein R1 to R5 are each independently a hydrogen atom that binds to a carbon atom constituting the skeleton of the cyclopentadienyl ring; a C1-C20 hydrocarbyl group; or a substituted metalloid group in which a C1-C20 hydrocarbyl group, an amide group, a phosphide group, and/or an alkoxide group has/have been substituted, ※ is a bond with M1 to M4 (M1 to M3 in the case of formula (1A)), and two to five of R1 to R5 are the hydrocarbyl group or substituted metalloid group, and wherein one of the carbon atoms constituting the skeleton of the cyclopentadienyl ring may be substituted by a 14th-group atom (excluding a carbon atom and a lead atom) or a 15th-group atom.

3. The complex as set forth in claim 2 , wherein, in formula (2), all of R1 to R5 are methyl groups, or four of R1 to R5 are methyl groups and the other one of R1 to R5 is a trialkylsilyl group.

4. The complex as set forth in claim 1 , wherein each of M1 to M4 (M1 to M3 in the case of formula (1A)) of formulas (1A) and (1B) is Ti.

5. A complex as set forth in claim 1 , the complex being represented by formula (1A).

6. A complex having nitrogen atoms incorporated therein by bringing a complex as set forth in claim 1 and nitrogen molecules into contact with each other.

7. The complex as set forth in claim 6 , the complex being a complex represented by formula (3) or a cationic or anionic complex from the complex:

wherein M1 to M3 and L1 to L3 are identical to those of formula (1A), X1 to X3 are each —H— or —N(H)—, and one or two of X1 to X3 are —N(H)—, and in one or more —N(H)—'s, H may be substituted by a boryl group, a silyl group, or an alkyl group.

8. A complex represented by formula (3′) or a cationic or anionic complex from the complex:

wherein M1 to M3 are each independently Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W, L1 to L3 are each independently a ligand selected from the group consisting of a ligand (Cp) including a substituted or unsubstituted cyclopentadienyl derivative, a diphenylamine ligand, a diphenylphosphine ligand, and a carboimideamide ligand, M5 is Cu, Zn, Sc, or Y, X is F, Cl, Br, I, or —OSO 2 CF 3 , and n (which indicates the number of X's) is an integer represented by p-3 (where p is the coordination number of M5).

9. A method for synthesizing ammonia, comprising the step of bringing hydrogen molecules and nitrogen molecules into contact with a complex as set forth in claim 1 .

10. A fixed bed for use in ammonia synthesis, comprising a complex as set forth in claim 1 , the complex being fixed.

11. A method for synthesizing ammonia, comprising the step of brining hydrogen molecules into contact with a complex as set forth in claim 6 .

12. A method for synthesizing ammonia, comprising the step of brining hydrogen molecules into contact with a complex as set forth in claim 7 .

13. A method for synthesizing ammonia, comprising the step of bringing hydrogen molecules and nitrogen molecules into contact with a complex as set forth in claim 8 .

14. A fixed bed for use in ammonia synthesis, comprising a complex as set forth in claim 6 , the complex being fixed.

15. A fixed bed for use in ammonia synthesis, comprising a complex as set forth in claim 7 , the complex being fixed.

16. A fixed bed for use in ammonia synthesis, comprising a complex as set forth in claim 8 , the complex being fixed.

Assignees

• Riken

Inventors

• Hou Zhaomin
• Shima Takanori
• Hu Shaowei
• Endo Yoshinori

Classifications

• C07F7/003

  without C-Metal linkages · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J2531/0222

  Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12 · CPC title

• C07F9/5022

  Aromatic phosphines (P-C aromatic linkage) · CPC title

• C07F7/28 Primary

  Titanium compounds · CPC title