Substituted mononuclear ruthenium complexes for catalysis of synthetic organic reactions

Patent metadata

Field	Value
Publication number	US-9782762-B2
Application number	US-201414771765-A
Country	US
Kind code	B2
Filing date	Feb 26, 2014
Priority date	Mar 1, 2013
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound.

In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO and phosphine. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.

First claim

The invention claimed is:

1. A mononuclear ruthenium complex having formula (1):

wherein:
m is 2;
n is 2; and
formula (1) is selected from the group consisting of:

wherein:
each L is independently molecular hydrogen, N(R) 3 , RC(═NR)R, pyrrolyl, imidazolyl, pyridinyl, pyrimidinyl, oxazolinyl, isoxazolinyl, As(R) 3 , ROH, RSH, ROR, RSR, RC≡N, RN≡C, RC(O)H, RC(O)R, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl or R 1 R 2 R 3 SiH;
each R is independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or alkyl, aryl, aralkyl, organooxy, monoorganoamino, diorganoamino, monoorganophosphino, diorganophosphino, monoorganosilyl, diorganosilyl, triorganosilyl or organothio, each of which is independently and optionally substituted with X;
R 17 , R 18 , R 19 and R 20 are each independently hydrogen, halogen, C 1 -C 10 alkyl or C 1 -C 10 alkoxy;
R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 aralkyl or C 6 -C 20 aryl; and
X is halogen, organooxy, monoorganoamino, diorganoamino or organothio;

with the proviso that two L may bond together.

2. The mononuclear ruthenium complex of claim 1 , wherein:
each L is independently RSH, RSR or R 1 R 2 R 3 SiH.

3. The mononuclear ruthenium complex of claim 2 , wherein:
each L is independently R 1 R 2 R 3 SiH, wherein R 1 R 2 R 3 SiH in one L is represented by R 7 R 8 R 9 SiH and R 1 R 2 R 3 SiH in the other L is represented by R 10 R 11 R 12 SiH;
R 7 , R 8 and R 9 are each independently alkyl, aryl or aralkyl;
R 10 , R 11 and R 12 are each independently alkyl, aryl or aralkyl; and
(i) one pair of R 7 , R 8 and R 9 , taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH 2 ) k —NH—, —NR—(CH 2 ) k —NR—, —PH—(CH 2 ) k —PH—, —PR—(CH 2 ) k —PR—, —CH═CH—, —CR═CR—, C 1 -C 10 alkylene, C 6 -C 30 arylene, C 7 -C 30 aralkylene, —(CH 2 O) k —, (CH 2 O) k —O—(CH 2 ) k —, —O—(CH 2 O) k —O—, —R′—O—(CH 2 O) k —O—R′—, —(CH 2 S) k —, (CH 2 ) k —S—(CH 2 ) k —, —S—(CH 2 ) k —S—, —R′—S—(CH 2 ) k —O—R′—, —Si(R) 2 — and —(CH 2 ) k —Si(R) 2 —(CH 2 ) k —; or
(ii) one pair of R 10 , R 11 and R 12 , taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH 2 ) k —NH—, —NR—(CH 2 ) k —NR—, —PH—(CH 2 ) k —PH—, —PR—(CH 2 ) k —PR—, —CH═CH—, —CR═CR—, C 1 -C 10 alkylene, C 6 -C 30 arylene, C 7 -C 30 aralkylene, —(CH 2 O) k —, (CH 2 O) k —O—(CH 2 ) k —, —O—(CH 2 O) k —O—, —R′—O— (CH 2 O) k —O—R′—, —(CH 2 S) k —, (CH 2 ) k —S—(CH 2 ) k —, —S—(CH 2 ) k —S—, —R′—S(CH 2 ) k —O—R′—, —Si(R) 2 — and —(CH 2 ) k —Si(R) 2 —(CH 2 ) k —;
each R is independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
each R′ is independently C 1 -C 10 alkylene; and
each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10.

4. The mononuclear ruthenium complex of claim 3 , wherein:
one pair of R 7 , R 8 and R 9 , taken together, form a crosslinking substituent.

5. The mononuclear ruthenium complex of claim 4 , wherein:
formula (1) is represented by:

6. The mononuclear ruthenium complex of claim 2 , wherein:
(a) (i) one L is RSH, wherein RSH is represented by R 13 SH or R 14 SH, and the other L is RSR, wherein RSR is represented by R 15 SR 16 , or (ii) one L is RSR, wherein RSR is represented by R 13 SR 14 , and the other L is RSH, wherein RSH is represented by R 15 SH or R 16 SH;
R 13 and R 14 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
R 15 and R 16 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl; and
at least one pair of any one of R 13 and R 14 and any one of R 15 and R 16 , taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH 2 ) k —NH—, —NR—(CH 2 ) k —NR—, —PH—(CH 2 ) k —PH—, —PR—(CH 2 ) k —PR—, —CH═CH—, —CR═CR—, C 1 -C 10 alkylene, C 6 -C 30 arylene, C 7 -C 30 aralkylene, —(CH 2 O) k —, (CH 2 O) k —O—(CH 2 ) k —, —O—(CH 2 O) k —O—, —R′—O—(CH 2 O) k —O—R′—, —(CH 2 S) k —, (CH 2 ) k —S—(CH 2 ) k —, —S—(CH 2 ) k —S—, —R′—S—(CH 2 ) k —O—R′—, —Si(R) 2 — and —(CH 2 ) k —Si(R) 2 —(CH 2 ) k —;
each R is independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
each R′ is independently C 1 -C 10 alkylene; and
each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10; or

(b) one L is RSH, wherein RSH is represented by R 13 SH or R 14 SH, and the other L is RSH, wherein RSH is represented by R 15 SH or R 16 SH;
R 13 and R 14 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
R 15 and R 16 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl; and
at least one pair of any one of R 13 and R 14 and any one of R 15 and R 16 , taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH 2 ) k —NH—, —NR—(CH 2 ) k —NR—, —PH—(CH 2 ) k —PH—, —PR—(CH 2 ) k —PR—, —CH═CH—, —CR═CR—, C 1 -C 10 alkylene, C 6 -C 30 arylene, C 7 -C 30 aralkylene, —(CH 2 O) k —, (CH 2 O) k —O—(CH 2 ) k —, —O—(CH 2 O) k —O—, —R′—O—(CH 2 O) k —O—R′—, —(CH 2 S) k —, (CH 2 ) k —S—(CH 2 ) k —, —S—(CH 2 ) k —S—, —R′—S—(CH 2 ) k —O—R′—, —Si(R) 2 — and —(CH 2 ) k —Si(R) 2 —(CH 2 ) k —;
each R is independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
each R′ is independently C 1 -C 10 alkylene; and
each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10; or

(c) one L is RSR, wherein RSR is represented by R 13 SR 14 , and the other L is RSR, wherein RSR is represented by R 15 SR 16 ;
R 13 and R 14 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
R 15 and R 16 are each independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl; and
at least one pair of any one of R 13 and R 14 and any one of R 15 and R 16 , taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH 2 ) k —NH—, —NR—(CH 2 ) k —NR—, —PH—(CH 2 ) k —PH—, —PR—(CH 2 ) k —PR—, —CH═CH—, —CR═CR—, C 1 -C 10 alkylene, C 6 -C 30 arylene, C 7 -C 30 aralkylene, —(CH 2 O) k —, (CH 2 O) k —O—(CH 2 ) k —, —O—(CH 2 O) k —O—, —R′—O—(CH 2 O) k —O—R′—, —(CH 2 S) k —, (CH 2 ) k —S—(CH 2 ) k —, —S—(CH 2 ) k —S—, —R′—S—(CH 2 ) k —O—R′—, —Si(R) 2 — and —(CH 2 ) k —Si(R) 2 —(CH 2 ) k —;
each R is independently C 1 -C 30 alkyl, C 6 -C 30 aryl or C 7 -C 30 aralkyl;
each R′ is independently C 1 -C 10 alkylene; and
each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10.

7. The mononuclear ruthenium complex of claim 6 , wherein:
(a) (i) one L is RSH, wherein RSH is represented by R 13 SH or R 14 SH, and the other L is RSR, wherein RSR is represented by R 15 SR 16 , or (ii) one L is RSR, wherein RSR is represented by R 13 SR 14 , and the other L is RSH, wherein RSH is represented by R 15 SH or R 16 SH; and
at least one pair of any one of R 13 and R 14 and any one of R 15 and R 16 , taken together, form a crosslinking substituent; or

(b) one L is RSH, wherein RSH is represented by R 13 SH or R 14 SH, and the other L is RSH, wherein RSH is represented by R 15 SH or R 16 SH; and
at least one pair of any one of R 13 and R 14 and any one of R 15 and R 16 , taken together, form a crosslinking substituent.

8. The monon

Assignees

• Univ Kyushu Nat Univ Corp
• Shinetsu Chemical Co

Inventors

• Nagashima Hideo
• Sunada Yusuke
• Tsutsumi Hironori
• Hashimoto Toru
• Sakuta Koji

Classifications

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C07C211/29

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title

• C07C217/58

  with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain · CPC title

• C07C15/18

  containing at least one group with formula[IMAGE cpc-sch-C07C-0954.gif] · CPC title

• C07C2531/22

  Organic complexes · CPC title