Hydrosilylation iron catalyst

Patent metadata

Field	Value
Publication number	US-10239896-B2
Application number	US-201515504736-A
Country	US
Kind code	B2
Filing date	Aug 19, 2015
Priority date	Aug 19, 2014
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

A hydrosilylation iron catalyst prepared from a two-electron ligand (L) and a mononuclear, binuclear, or trinuclear complex of iron indicated by formula (1), Fe having bonds with carbon atoms included in X and the total number of Fe-carbon bonds being 2-10. As a result of using iron, the hydrosilylation iron catalyst is advantageous from a cost perspective as well as being easily synthesized. Hydrosilylation reactions can be promoted under mild conditions by using this catalyst.

Fe(X) a   (1)

(in the formula, each X independently indicates a C2-30 ligand that may include an unsaturated group excluding carbonyl groups (CO groups) and cyclopentadienyl groups, however at least one X includes an unsaturated group, a indicates an integer of 2-4 per Fe atom.)

First claim

The invention claimed is:

1. A hydrosilylation iron catalyst which is prepared from a two-electron ligand (L) and a mono-, bi- or tri-nuclear complex of iron having the formula (1):
Fe(X) a   (1)

wherein
each X is independently a C 2 -C 30 ligand which may contain an unsaturated group, exclusive of carbonyl (CO) and cyclopentadienyl groups, at least one X contains an unsaturated group,
a is an integer of 2 to 4 per Fe atom, and
Fe has bonds with carbon atoms in X, the total number of Fe-carbon bonds being 2 to 10, and Fe bonds solely with carbon atoms in X.

2. A hydrosilylation iron catalyst consisting of a mixture of a two-electron ligand (L) and a mono-, bi- or tri-nuclear complex of iron having the formula (1):
Fe(X) a   (1)

wherein
each X is independently a C 2 -C 30 ligand which may contain an unsaturated group, exclusive of carbonyl (CO) and cyclopentadienyl groups, at least one X contains an unsaturated group,
a is an integer of 2 to 4 per Fe atom, and
Fe has bonds with carbon atoms in X, the total number of Fe-carbon bonds being 2 to 10.

3. The hydrosilylation iron catalyst of claim 1 or 2 wherein each X is a C 2 -C 30 ligand containing an unsaturated group.

4. The hydrosilylation iron catalyst of claim 1 wherein X is an aryl group, and the total number of Fe-carbon bonds is 2.

5. The hydrosilylation iron catalyst of claim 1 which is a mononuclear complex wherein the total number of Fe-carbon bonds is 6 to 10.

6. The hydrosilylation iron catalyst of claim 5 wherein the total number of Fe-carbon bonds is 10.

7. The hydrosilylation iron catalyst of claim 5 or 6 wherein X is at least one ligand selected from a cyclic olefin, acyclic olefin, cyclic olefinyl and acyclic olefinyl group having 1 to 5 unsaturated groups in the molecule.

8. The hydrosilylation iron catalyst of claim 1 wherein L is at least one two-electron ligand selected from the group consisting of carbonyl, molecular hydrogen, amine, imine, nitrogen-containing heterocycle, phosphine, arsine, alcohol, thiol, ether, sulfide, nitrile, isocyanide, aldehyde, ketone, and carbene.

9. The hydrosilylation iron catalyst of claim 8 wherein L is at least one two-electron ligand selected from the group consisting of molecular hydrogen, amine, imine, nitrogen-containing heterocycle, phosphine, arsine, alcohol, thiol, ether, sulfide, nitrile, isocyanide, aldehyde, ketone, and carbene.

10. The hydrosilylation iron catalyst of claim 9 wherein L is at least one two-electron ligand selected from the group consisting of nitrogen-containing heterocycle, isocyanide, and carbene.

11. The hydrosilylation iron catalyst of claim 10 wherein L is at least one two-electron ligand selected from
an isocyanide compound having the formula (2):
Y—NC  (2)

wherein Y is an optionally substituted C 1 -C 30 monovalent organic group which may be separated by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus, and
a carbene compound having one or two adjoining nitrogen atoms, represented by the formula (3):

wherein Z is a carbon, nitrogen or oxygen atom, b is 3 when Z is a carbon atom, b is 2 when Z is a nitrogen atom, b is 1 when Z is an oxygen atom, R 1 and R 2 are each independently a C 1 -C 30 alkyl, aryl or aralkyl group which may be substituted with a halogen atom or alkoxy group, any one of R 1 and any one of R 2 may bond together to form a divalent organic group so that the compound has a cyclic structure, and the compound having a cyclic structure may contain a nitrogen atom and/or unsaturated bond.

12. The hydrosilylation iron catalyst of claim 11 wherein the carbene compound of formula (3) has the formula (4):

wherein A is a C 2 -C 5 divalent organic group which may contain a nitrogen atom and/or unsaturated bond, R 1 and R 2 are each independently a C 1 -C 30 alkyl, aryl or aralkyl group which may be substituted with a halogen atom or alkoxy group.

13. The hydrosilylation iron catalyst of claim 10 wherein L is a bisiminopyridine compound or terpyridine compound.

14. The hydrosilylation iron catalyst of claim 1 which is prepared in a system where hydrosilylation reaction of a compound having an aliphatic unsaturated bond with a hydrosilane compound having a Si—H group or organohydropolysiloxane compound is carried out.

15. A method for preparing an addition compound comprising the step of carrying out hydrosilylation reaction of a compound having an aliphatic unsaturated bond with a hydrosilane compound having a Si—H bond or organohydropolysiloxane compound in the presence of the hydrosilylation iron catalyst of claim 1 .

16. The method for preparing an addition compound of claim 15 wherein the compound having an aliphatic unsaturated bond is an organopolysiloxane having an alkenyl group.

Assignees

• Univ Kyushu Nat Univ Corp
• Shinetsu Chemical Co

Inventors

• Nagashima Hideo
• Sunada Yusuke
• Noda Daisuke
• SOEJIMA Hiroe
• Sakuta Koji

Classifications

• C07F7/18

  Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages · CPC title

• B01J2531/0205

  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 title

• B01J31/181

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine · CPC title

• C07F7/0829

  Hydrosilylation reactions · CPC title

• C07F15/02

  Iron compounds · CPC title