Catalyst ligands, catalytic metal complexes and processes...

Details Catalyst ligands, catalytic metal complexes and processes... Catalyst ligands, catalytic metal complexes and processes...

2001-03-21

2001-11-13

Killos, Paul J. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C560S238000, C564S305000

Reexamination Certificate

active

06316663

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to new organic compounds (e.g., ligands), their metal complexes and compositions using those compounds; the invention also relates to the field of catalysis. In particular, this invention relates to new compounds which when combined with suitable metals or metal precursor compounds provide useful catalysts for various bond-forming reactions, including polymerizations and small molecule transformations. The invention also relates to combinatorial chemistry in that combinatorial techniques were used in connection with creating the ligands and testing compositions containing the ligands.
BACKGROUND OF THE INVENTION
Ancillary (or spectator) ligand-metal coordination complexes (e.g., organometallic complexes) and compositions are useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents and drugs. Ancillary ligand-metal coordination complexes of this type can be prepared by combining an ancillary ligand with a suitable metal compound or metal precursor in a suitable solvent at a suitable temperature. The ancillary ligand contains functional groups that bind to the metal center(s), remain associated with the metal center(s), and therefore provide an opportunity to modify the steric, electronic and chemical properties of the active metal center(s) of the complex.
Certain known ancillary ligand-metal complexes and compositions are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilylation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, carbon-halogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions and other transformations. See, e.g., U.S. Pat. Nos. 5,576,460 and 5,550,236, both of which are incorporated herein by reference.
One example of the use of these types of ancillary ligand-metal complexes and compositions is in the field of polymerization catalysis. In connection with single site catalysis, the ancillary ligand offers opportunities to modify the electronic and/or steric environment surrounding an active metal center. This allows the ancillary ligand to create possibly different polymers. Ancillary ligands and ancillary metal complexes that are similar to those disclosed herein have been discussed in WO 98/30609, incorporated herein by reference for all purposes. However, that application does not specifically disclose any of the ligands, complexes or compositions disclosed herein and does not disclose any method of making the ligands (i.e., the ancillary ligands) of this invention.
It is always a desire to discover new ancillary ligands, which upon coordination to a metal center or addition of a metal compound or precursor will catalyze or assist in catalysis of reactions differently from known ligand systems. This invention provides new ancillary ligands that may be used for coordination to a metal center or included in a composition with a metal or metal precursor compound. Upon coordination to the metal center or inclusion in the composition, such ligands influence the electronic and steric environment of the resulting coordination complex and may catalyze reactions differently, including more efficiently and selectively than known systems.
SUMMARY OF THE INVENTION
In a first aspect, the invention disclosed herein is a new ligand (i.e., an ancillary ligand), which can be characterized by the general formula:
wherein each R
1
, R
2
, R
3
, R
4
and R
6
is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, optionally, R
1
and R
2
are joined together in a ring structure and/or R
3
and R
4
are joined together in a ring structure and/or R
1
and R
6
are joined together in a ring structure; and b is 0, 1, 2, 3 or 4. Where b is at least 2, two R
6
groups may be joined in a fused ring structure with the benzene ring in the backbone of the ligand. G is either oxygen or nitrogen. When G is oxygen, a is 0. When G is nitrogen, a is 1.
In a second aspect, this invention is a compound characterized by the general formula:
wherein each R
1
, R
2
, R
3
, R
4
, R
5
and R
6
is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, optionally, R
1
and R
2
are joined together in a ring structure and/or R
3
and R
4
are joined together in a ring structure and/or R
4
and R
5
are joined together in a ring structure and/or R
1
and R
6
are joined together in a ring structure; G is either oxygen or nitrogen and a is either 1 or 2 depending on G; and b is 0, 1, 2, 3 or 4. When G is nitrogen and a is 2, the two R
3
groups may also join to form a ring structure.
This invention also relates to a novel method of making these new ligands. The general method of making these ligands is to start with a compound characterized by the general formula:
wherein R
4
and R
6
are as defined above and X is selected from the group consisting of chloro, bromo, iodo, triflate, tosylate and nonaflate; and R
8
and R
9
are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof. This compound is reacted with an amine characterized by the general formula HNR
1
R
2
, where R
1
and R
2
are as defined above. This provides ligands within the second aspect. Optionally, an acetyl or ketal functionality of the product is then hydroylzed, providing ligands within the first aspect. Thereafter, the product can be reacted with a primary or secondary amine to transform the ligand. Hydrogenation is thereafter an optional step. All steps may or may not be performed using parallel or high throughput or combinatorial methods.
In yet another aspect, this invention provides new metal-ligand complexes or compositions comprising the new ligands and a metal precursor. For catalysis, the ligands can be included in a composition including a suitable metal or metal precursor compound that can be of the form ML
n
, where the composition has catalytic properties. Also, the ligands can be coordinated with a metal precursor to form metal-ligand complexes, which may be catalysts. Depending on the groups chosen for R
1
, R
2
and R
3
in the ligand (i.e., prior to reaction with the metal precursor), the metal-ligand complexes can be characterized by one of many different general formulas depending on how the ligand attaches to or associates with the metal.
A further aspect of this invention provides for the novel ligands, compositions or complexes to be created and tested in a combinatorial manner. Thus, the ligands, compositions or complexes may be in an array with each ligand, composition or complex in a different region of a substrate. The number of ligands, compositions or complexes on a single substrate will vary according to the desired density, but will typically have at least 10 ligands, compositions or complexes on a single substrate.
These metal-ligand complexes or compositions catalyze polymerization and copolymerization reactions, particularly with monomers that are olefins, diolefins or otherwise acetylenically unsaturated. Other reactions that can be catalyzed include activation of and/or formation of H—Si, H—H, H—N, H—O, H—P, H—S, C—H, C—C, C═C, C≡C, C-halogen, C—N, C—O, C—S, C—

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