Divalent lanthanide reduction catalysts
View Patent ↗The present invention relates generally to the chemistry of inorganic reduction catalysts, and more particularly to the composition and use of dihalogenated lanthanides catalysts, for example TmI 2 or DyI 2 , to facilitate reduction reactions such as the preparation of alkylated hydrocarbons and/or organic polymers.
1. A method of reducing a compound to form a reduction product, said method comprising the step of combining the compound with a lanthanide catalyst having the formula:
G 1 —M—G 2
wherein;
M is either a Dysprosium or a Neodymium;
G 1 and G 2 are chemical entities independently selected from the group consisting of a halogen, an alkyl, an aryl, an NR 2 , an OR 2 , a PR 2 and an SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.
2. A method according to claim 1 wherein G 1 is an Iodine.
3. A method according to claim 1 wherein G 2 is an Iodine.
4. A method according to claim 1 wherein G 1 and G 2 are the same halogen.
5. A method according to claim 1 wherein G 1 and G 2 are different halogens.
6. A method according to claim 1 wherein M is a Neodymium and G 1 and G 2 are iodines.
7. A method according to claim 1 wherein M is a Dysprosium and G 1 and G 2 are iodines.
8. A method according to claim 1 wherein M is complexed with at least one solvent molecule, S.
9. A method according to claim 8 wherein the solvent molecule comprises a Lewis base.
10. A method according to claim 9 wherein the Lewis base is a heteroatom donor base.
11. A method according to claim 9 wherein the Lewis base is selected from the group consisting of di-alkyl-oxy-ethanes, tetrahydrofuran, dienes, nitriles and ethers.
12. A method according to claim 9 wherein the Lewis base comprises a di-alkyl-oxy-ethane.
13. A method according to claim 9 wherein the Lewis base comprises a dimethoxyethane.
14. A method according to claim 8 wherein the complex has the general Formula B:
wherein;
M either a Dysprosium or a Neodymium;
G 1 and G 2 are chemical entities independently selected from the group consisting of a halogen, an alkyl, an aryl, an NR 2 , an OR 2 , a PR 2 and an SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms; and,
S is dimethoxyethane (DME).
15. A method according to claim 14 wherein M is a Neodymium G 1 and G 2 are Iodine and S is dimethoxyethane.
16. A method according to claim 14 wherein M is Dysprosium, G 1 and G 2 are Iodine, and S is dimethoxyethane.
17. A method according to claim 1 wherein the compound is an organic compound, the lanthanide catalyst effects alkylation of the compound, and the reduction product is an alkylated organic compound.
18. A method according to claim 17 wherein the lanthanide catalyst is a Thulium diiodide.
19. A method according to claim 17 wherein the lanthanide catalyst effects alkylation of the organic compound with RJ, wherein R is an alkyl and J is a halogen selected from the group consisting of Iodine, Bromine, Chlorine and Fluorine.
20. A method according to claim 19 wherein G 1 and G 2 are Bromine.
21. A method according to claim 19 wherein G 1 and G 2 are Chlorine.
22. A method according to claim 1 wherein the compound comprises a polymerizable unit and the reduced product is a polymer.
23. A method according to claim 22 wherein the M is a Dysprosium, G 1 and G 1 are Iodine.
24. A method according to claim 22 wherein the polymerizable unit comprises isoprene.
25. A polymeric reduction product made from a process comprising the step of combining a compound which comprises a polymerizable unit with a lanthanide catalyst having the general Formula A:
G 1 —M—G 2
wherein;
L is a lanthanide other than the Europium, Ytterbium or Samarium;
G 1 and G 2 are chemical entities independently selected from the group consisting of a halogen, an alkyl, an aryl, an NR 2 , an OR 2 , a PR 2 and an SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.
26. A reduction product according to claim 25 wherein the M is a Dysprosium, G 1 and G 2 are Iodine.
27. A reduction product according to claim 25 wherein the polymerizable unit comprises isoprene.
28. A method for making a dihalogenated lanthanide compound, said method comprising the steps of:
combining a Dysprosium metal with a halogen;
reacting the Dysprosium metal with the halogen to form an initial mixture; and
heating the initial mixture for about 1 to about 60 minutes.
29. A method according to claim 28 wherein the halogen is selected from the group consisting of Iodine, Bromine, Chlorine and Fluorine.
30. A method according to claim 28 wherein the halogen is Iodine.
31. A method according to claim 28 wherein the heating is for about 2 to about 30 minutes.
32. A method according to claim 28 wherein the halogen is selected from the group consisting of Iodine, Bromine, Chlorine and Fluorine.
33. A method according to claim 28 wherein the halogen is Iodine.
34. A method according to claim 28 wherein the solvent molecule S comprises a Lewis base.
35. A method according to claim 28 wherein the Lewis base is selected from the group consisting of di-alkyl-oxy-ethanes, tetrahydrofuran, dienes, nitriles and ethers.
36. A method according to claim 28 wherein the Lewis base comprises a dimethoxyethane.
37. A method of reducing a compound to form a pollmeric reduction product, said method comprising the step of combining the compound which comprises a polymerizable unit with a lanthanide catalyst having the formula:
G 1 —M—G 2
wherein;
M is a lanthanide other than the Europium, Ytterbium or Samarium;
G 1 and G 2 are chemical entities independently selected from the group consisting of a halogen, an alkyl, an aryl, an NR 2 , an OR 2 , a PR 2 and an SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.
38. A method according to claim 37 wherein M is selected from the group consisting of Thulium, Dysprosium, Neodymium, Cerium, Praseodymium, Gadolinium, Terbium, Holmium, Erbium, Lutetium, Lanthanum and Yttrium.
39. A method according to claim 37 wherein the M is a Thulium.
40. A method according to claim 37 wherein the M is a Dysprosium.
41. A method according to claim 37 wherein the M is a Neodymium.
42. A method according to claim 37 wherein G 1 is an Iodine.
43. A method according to claim 37 wherein G 2 is an Iodine.
44. A method according to claim 37 wherein G 1 and G 2 are the same halogen.
45. A method according to claim 37 wherein G 1 and G 2 are different halogens.
46. A method according to claim 37 wherein M is a Thulium and G 1 and G 2 are iodines.
47. A method according to claim 37 wherein M is a Dysprosium and G 1 and G 2 are iodines.
48. A method according to claim 37 wherein M is complexed with at least one solvent molecule, S.
49. A method according to claim 48 wherein the solvent molecule comprises a Lewis base.
50. A method according to claim 49 wherein the Lewis base is a heteroatom donor base.
51. A method according to claim 49 wherein the Lewis base is selected from the group consisting of di-alkyl-oxy-ethanes, tetrahydrofuran, dienes, nitrites and ethers.
52. A method according to claim 49 wherein the Lewis base comprises a di-alkyl-oxy-ethane.
53. A method according to claim 49 wherein the Lewis base comprises a dimethoxyethane.
54. A method according to claim 48 wherein the complex has the general Formula B:
wherein;
M is a lanthanide other than the Europium, Ytterbium or Samarium;
G 1 and G 2 are chemical entities independently selected from the group consisting of a halogen, an alkyl, an aryl, an NR 2 , an OR 2 , a PR 2 and an SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms; and,
S is dimethoxyethane (DME).
55. A method according to claim 54 wherein M is Thulium, G 1 and G 2 are Iodine and S is dimethoxyethane.
56. A method according to claim 54 wherein M is Dysprosium, G 1 and G 2 are Iodine, and S is dimethoxyethane.
57. A method according to claim 37 wherein the compound is an organic compound, the lanthanide catalyst effects alkylation of the compound, and the reduction product is an alkylated organic compound.
58. A method according to claim 57 wherein the lanthanide catalyst is a Thulium diiodide.
59. A method according to claim 57 wherein the lanthanide catalyst effects alkylation of the organic compound with RJ, wherein R is an alkyl and J is a halogen selected from the group consisting of Iodine, Bromine, Chlorine and Fluorine.
60. A method according to claim 59 wherein G 1 and G 1 are Bromine.
61. A method according to claim 59 wherein G 1 and G 2 are Chlorine.
62. A method according to claim 59 wherein the M is a Dysprosium, G 1 and G 2 are Iodine.
63. A method according to claim 59 wherein the polymerizable unit isoprene.