Catalytic ammonia synthesis by transition metal molecular complexes

Patent metadata

Field	Value
Publication number	US-9815694-B2
Application number	US-201414515716-A
Country	US
Kind code	B2
Filing date	Oct 16, 2014
Priority date	Oct 16, 2013
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

This invention relates to molecular catalysts and chemical reactions utilizing the same, and particularly to catalysts and catalytic methods for reduction of molecular nitrogen. The molecular catalytic platform provided herein is capable of the facile reduction of molecular nitrogen under useful conditions such as room temperature or less and atmospheric pressure or less.

First claim

We claim:

1. A catalytic process for reduction of molecular nitrogen (N 2 ) to generate a reduction product, said process comprising the steps of:
contacting a transition metal catalyst with a source of protons and a source of electrons in the presence of said molecular nitrogen, thereby generating said reduction product;
wherein said transition metal catalyst comprises a metal complex comprising a transition metal atom selected from the group consisting of Fe and Co, and a phosphine ligand (L) having the formula (FX1A), (FX1B) or (FX1C):

wherein:
X 1 is B, C, Si or P;
each of L 1 , L 2 and L 3 is independently a substituted or unsubstituted C 1 -C 10 alkylene, C 3 -C 10 cycloalkylene, C 5 -C 10 arylene, or C 5 -C 10 heteroarylene;
each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is independently hydrogen or a substituted or unsubstituted C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 5 -C 8 aryl, C 5 -C 8 heteroaryl, C 1 -C 18 acyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, or —P(OR 8 ) 2 , wherein each R 8 is independently hydrogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 5 -C 8 aryl or C 5 -C 8 heteroaryl.

2. The catalytic process of claim 1 , wherein said metal complex further comprises N 2 and has the formula (FX2A), (FX2B) or (FX2C):

wherein Z is said transition metal atom.

3. The process of claim 1 , wherein said step of contacting said transition metal catalyst with said source of protons and said source of electrons in the presence of said molecular nitrogen further regenerates said transition metal catalyst.

4. The process of claim 1 , wherein said reduction product is NH 3 or N 2 H 4 .

5. The process of claim 1 , wherein said transition metal catalyst further comprises a N 2 group; wherein said transition metal catalyst has the formula: (L)Z(N 2 ) − (FX3); wherein L is said phosphine ligand and Z is said transition metal atom.

6. The process of claim 5 further comprising the step of protonating said transition metal catalyst so as to generate a hydrogenated metal-N 2 complex; wherein protonating occurs via contacting said transition metal catalyst with an acid.

7. The process of claim 6 , wherein said hydrogenated metal-N 2 complex has the formula (FX4), (FX5A) or (FX5B):
(L)Z(N x H y ) (FX4), (L)Z(NH 2 ) (FX5A) or (L)Z(NH 3 ) + (FX5B);
wherein x is 1 or 2; y is 1, 2, 3, 4 or 5; L is said phosphine ligand and Z is said transition metal atom.

8. The process of claim 6 , further comprising reductive protonation of said hydrogenated metal-N 2 complex, thereby generating said reduction product and regenerating said transition metal catalyst.

9. The process of claim 1 further comprising the step of:
providing a transition metal catalyst precursor comprising a precursor transition metal complex comprising said transition metal atom and said phosphine ligand (L); and
contacting said transition metal catalyst precursor with molecular nitrogen in the presence of an acid and a reductant, thereby generating said transition metal catalyst comprising a N 2 adduct of said transition metal catalyst precursor;
wherein said transition metal catalyst precursor has the formula:
(L)Z + (FX6);

wherein L is said phosphine ligand and Z is said transition metal atom.

10. The process of claim 9 , wherein said transition metal catalyst is generated via reduction of said transition metal catalyst precursor wherein said reducing agent is Na, Na/Hg or KC 8 .

11. The process of claim 1 , wherein said transition metal catalyst is a mononuclear metal complex, wherein said transition metal atom is Fe and characterized by an oxidation state of Fe(−1), Fe(0), Fe(I), Fe(II), Fe(III), or Fe(IV).

12. The process of claim 1 , wherein said phosphine ligand is a tripodal trisphosphine ligand having a boron, carbon, silicon or phosphorous axial donor atom.

13. The process of claim 1 , wherein said phosphine ligand has an aryl backbone comprising at least one of L 1 , L 2 and L 3 independently comprising C 5 -C 10 arylene or C 5 -C 10 heteroarylene or wherein said phosphine ligand comprises one or more cyclohexylamine ring systems.

14. The process of claim 1 , wherein said ligand of said transition metal catalyst has the formula (FX7A), (FX7B) or (FX7C):

15. The process of claim 14 , wherein said metal complex further comprises N 2 and has the formula (FX8A), (FX8B) or (FX8C):

wherein Z is said transition metal atom.

16. The process of claim 1 , wherein said ligand of said transition metal catalyst has the formula (FX9A), (FX9B) or (FX9C):

17. The process of claim 1 , wherein said ligand of said transition metal catalyst has formula (FX10A), (FX10B) or (FX10C):

wherein i Pr is isopropyl, Ph is phenyl and Cy is cyclohexyl.

18. The process of claim 1 , wherein said ligand of said transition metal catalyst has formula (FX10A), (FX10B), (FX10C) or (FX10D):

wherein iPr is isopropyl, Ph is phenyl and Cy is cyclohexyl.

19. The process of claim 1 , wherein said transition metal catalyst has the formula [(TP R B)Fe(N 2 )] − , [(CP R 3 )Fe(N 2 )] − , [(SiP R 3 )Fe(N 2 )] − , [(TP R B)Co(N 2 )] − , [(CP R 3 )Co(N 2 )] − , or [(SiP R 3 )Co(N 2 )] − , wherein TP R B is a tris(phosphinoaryl)borane ligand, CP R 3 is a tris(phosphinoaryl)alkyl ligand and SiP R 3 is tris(phosphinoaryl)silyl ligand.

20. The process of claim 1 , wherein at least one of said molecular nitrogen said transition metal catalyst, said source of protons and said source of electrons are provided in a solution comprising one or more solvents, wherein the concentration of said molecular nitrogen in said solution is selected from the range of 1×10 −4 M to 1 M wherein the concentration of said transition metal catalyst in said solution is selected from the range of 0.01 mM to 10 mM.

21. The process of claim 1 , wherein said source of protons is one or more acids selected from the group consisting of: HBAr F 4 (hydro tetrakis[(3,5-trifluoromethyl)phenyl]borate), HOTf (triflic acid), HX, HBF 4 , ArNH 3 +X and a combination of these; wherein X is a halogen.

22. The process of claim 21 , wherein the concentration of said one or more acids is selected from the range of 0.01-5 M.

23. The process of claim 1 , wherein said source of electrons is one or more reductants selected from the group consisting of Na, K/Hg, KC 8 , Na/Hg, NaBH 4 − , Mg, Zn and any combination of these.

24. The process of claim 23 , wherein the concentration of said one or more reductants is selected from the range of 0.1-100 M.

25. The process of claim 20 , wherein said transition metal catalyst is a homogeneous catalyst, wherein said transition metal catalyst, said source of protons, said source of electrons and said mo

Assignees

• California Inst Of Techn

Inventors

• Peters Jonas C
• Anderson John S
• Cruetz Sidney E
• Rittle Jonathan D

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• B01J2531/0247

  Tripodal ligands, e.g. comprising the tris(pyrazolyl)borate skeleton, "tpz", neutral analogues thereof by CH/BH exchange or anionic analogues of the latter by exchange of one of the pyrazolyl groups for an anionic complexing group such as carboxylate or -R-Cp · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• C01C1/026

  Preparation of ammonia from inorganic compounds · CPC title

• B01J2531/842

  Iron · CPC title