Transition metal complexes, their preparation and use

Patent metadata

Field	Value
Publication number	US-9701703-B2
Application number	US-201414893673-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	May 24, 2013
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

Novel transition metal complexes are provided which represent viable catalysts for a broad variety of reactions such as hydrogenation reactions and metathesis reactions. Novel preparation processes are made available via unprecedented routes inter alia not involving structures according to Grubbs I or Grubbs II catalysts.

First claim

The invention claimed is:

1. A complex having general formula (I)

wherein
M means Ru, Os or Fe;
X means O or S;
D means S, O, PR 2 , or NR 2 with R 2 meaning straight chain or branched C 1 -C 14 alkyl, C 3 -C 8 cycloalkyl, or C 6 -C 24 aryl;
Y means a divalent moiety or an unsubstituted or substituted C 6 -C 10 arylene group;
R means unsubstituted or substituted C 6 -C 14 aryl;
L 1 means a ligand;
Z means B, Al, Ga, or In;
R 1 are identical or different and represent F, Cl, Br, I, unsubstituted or substituted, straight chain or branched C 1 -C 14 alkyl, C 3 -C 8 cycloalkyl, or unsubstituted or substituted C 6 -C 24 aryl;
X 1 means F, Cl, Br, or I
L 2 is a two electron donor ligand; and
n Is either 0 or 1.

2. The complex according to claim 1 , wherein in general formula (I)
M means Ru
X means O or S;
D means S, O, PR 2 , or NR 2 with R 2 meaning straight chain or branched C 1 -C 6 alkyl, C 5 -C 6 cycloakyl, or C 6 -C 14 aryl
Y means a divalent moiety or an unsubstituted or substituted C 6 -C 10 arylene group;
R means unsubstituted or substituted C 6 -C 14 aryl;
L 1 means either
P(R 2 ) 3 wherein R 2 are identical or different and mean straight chain or branched C 1 -C 8 alkyl, C 6 -C 14 aryl, or C 3 -C 10 cycloalkyl, wherein each of the aforementioned groups may be substituted by one or more substituents selected from the group consisting of halogen, SO 3 Na, C 1 -C 8 -alkyl, the latter either unsubstituted or substituted by one or more F, Cl, Br or I, C 6 -C 14 aryl, and C 1 -C 5 -alkoxy; or
an N-heterocyclic carbene ligand of general formulae (IM-a) or (IM-b)

wherein
R 4 , R 5 , R 6 , R 7 are identical or different and are each hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloakyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 4 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 20 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 20 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 20 -arylsulphonate or C 1 -C 20 -alkylsulphinyl;

or in the alternative
R 6 and R 7 have the above mentioned meanings and at the same time R 4 and R 5 jointly form a C 6 -C 10 cyclic structure together with the two adjacent carbon atoms in the imidazoline or imidazolidine ring;

Z means B, Al, Ga, or In;
R 1 are identical or different and represent F, Cl, Br, I, unsubstituted or substituted, straight chain or branched C 1 -C 14 alkyl, C 3 -C 8 cycloalkyl, or unsubstituted or substituted C 6 -C 24 aryl;
X 1 means F, Cl, Br, or I
L 2 is a two electron donor ligand; and
n is either 0 or 1.

3. The complex according to claim 1 , wherein in general formula (I)
M means Ru;
X means O or S;
D means S, O, PR 2 , or NR 2 with R 2 meaning straight chain or branched C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, or C 6 -C 14 aryl
Y means 1,2-ethylene or 1,2-phenylene;
R means phenyl with none, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, and I;
L 1 is selected from the group consisting of PPh 3 , P(p-Tol) 3 , P(o-Tol) 3 , PPh(CH 3 ) 2 , P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , P(p-CF 3 C 6 H 4 ) 3 , P(C 6 H 4 —SO 3 Na) 3 , P(CH 2 C 6 H 4 —SO 3 Na) 3 , P(isopropyl) 3 , P(CH(CH 3 )CH 2 CH 3 ) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 , P(neophyl) 3 , and an N-heterocyclic carbene ligand of general formulae (IM-a) or (IM-b), wherein R 5 and R 7 are identical or different and represent i-propyl, neopentyl, adamantyl, mesityl or 2,6-diisopropylphenyl, and R 4 and R 5 are identical or different and represent hydrogen, C 6 -C 24 -aryl, straight-chain or branched C 1 -C 10 -alkyl, or together with the carbon atoms to which they are bound form a C 6 -C 10 cycloalkyl or C 6 -C 10 aryl substituent;
Z means B, Al, Ga, or In;
R 1 are identical or different and represent F, Cl, Br, or I;
X 1 means F, Cl, Br, or I;
L represents CH 3 CN, pyrdine or tetrahydrofuran; and
n is either 0 or 1.

4. The complex according to claim 1 , wherein in formula (I)
M means Ru
X means O or S;
D means S, O, PR 2 , or NR 2 with R 2 meaning straight chain or branched C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, or C 5 -C 14 aryl
Y means 1,2-ethylene or 1,2-phenylene;
R means phenyl with none or 5 substituents selected from the group consisting of F, Cl, Br, and I;
L 1 is selected from the group consisting of PPh 3 , P(p-To) 3 , P(o-Tol) 3 , PPh(CH 3 ), P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , P(P—CF 3 C 6 H 4 ) 3 , P(C 6 H 4 —SO 3 Na) 3 , P(CH 2 C 6 H 4 —SO 3 Na) 3 , P(isopropyl) 3 , P(CH(CH 3 )CH 2 CH 3 ) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 , P(neophyl) 3 , and N-heterocyclic carbene ligands of the structures (VIII-a) to (VIII-o)

Z means B;
R 1 are identical and represent Cl;
X 1 means Cl;
L 2 represents CH 3 CN, pyridine or tetrahydrofuran; and
n is either 0 or 1.

5. A process for preparing the complex according to claim 1 , the process comprising:
(1) reacting a complex of general formula (II)

wherein
M means Ru, Os or Fe;
X means O or S;
D means S, O, PR, or NR 2 with R 2 meaning straight chain or branched C 1 -C 14 alkyl, C 3 -C 8 cycloalkyl, or C 6 -C 24 aryl,
Y means a divalent moiety or an unsubstituted or substituted C 6 -C 10 arylene group;
R means unsubstituted or substituted C 6 -C 14 aryl;
L 1 means a ligand;

with a compound of general formula (III)
ZX 1 (R 1 ) 2   (III)

wherein
Z means B, Al, Ga or In;
X 1 means F, Cl, Br, or I; and
R 1 are identical or different and represent F, Cl, Br, I, unsubstituted or substituted, straight chain or branched C 1 -C 14 -alkyl, C 3 -C 8 cycloalkyl, or unsubstituted or substituted C 6 -C 24 aryl;

resulting in a complex according to general formula (IV)

and
(2) reacting the compound of general formula (IV) with a compound of general formula (V)
Z(R 1 ) 3   (V)

to obtain the complex catalyst according to general formula (I).

6. The process according to claim 5 , further including, to obtain complex catalyst according to general formula (I) with n being 1, adding the ligand L 2 simultaneously with or after addition of the compound of general formula (V) in step 2.

7. The process according to claim 5 , wherein:
M means Ru, Os or Fe;
X means O or S;
D means S, O, PR 2 , or NR 2 with R 2 meaning straight chain or branched C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, or phenylene;
Y means 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,2-phenylene, or 2,3-naphthylene;
R means phenyl with none, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, and I;
L 1 means an N-heterocyclic carbene ligand or a ligand P(R 2 ) 3 wherein R 2 means unsubstituted or substituted, straight chain or branched C 1 -C 14 alkyl, unsubstituted or substituted C 5 -C 24 aryl, or unsubstituted or substituted C 3 -C 20 cycloalkyl;
Z means B;
X 1 means Cl;

Assignees

• Lanxess Deutschland Gmbh
• Governing Council Univ Toronto
• Arlanxeo Deutschland Gmbh

Inventors

• Lund Clinton
• Stephan Douglas Wade
• Mckinty Adam
• Ong Christopher
• Boone Michael

Classifications

• B01J2231/324

  Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• C07F15/0046 Primary

  Ruthenium compounds · CPC title

• B01J2531/821

  Ruthenium · CPC title

• C08F136/20

  unconjugated · CPC title