Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
1998-04-17
2001-05-01
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C549S200000, C549S491000, C549S497000, C556S021000, C568S002000, C568S006000, C568S013000, C568S017000
Reexamination Certificate
active
06225487
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to new organic compounds, their metal complexes and compositions using those compounds; the invention also generally 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 C—N bond formation. 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.
One example of the use of these types of ancillary ligand-metal complexes and compositions is in the field of homogeneous catalysis to form a sp
2
C—N bond. A sp
2
C—N bond is a structural component in a variety of synthetic and naturally occurring biologically active compounds, polymers and dyes. Currently, existing methodologies are not general, in that different complexes or compositions are used for different substrates. Also, existing ligands are expensive. Thus there is a need for new, less expensive ligands that are generally applicable to all types of C—N bond formation, including sp
2
C—N bond formation.
Moreover, it is always a desire to discover new ancillary ligands, which upon coordination to a metal center will catalyze 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
The invention disclosed herein is a new ligand, which can be characterized by the general formula:
wherein
each R
1
, R
2
, R
3
, R
4
and R
5
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;
Q
1
and Q
2
are, independently, selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, Q
1
and Q
2
are joined together in a ring structure;
X is selected from the group consisting of C, H, O, P, Si, B and N atoms; and a is 0, 1, 2, or 3, depending on X;
Y is selected from the group consisting of N, P and O atoms; and b is 1 or 2, depending on Y; and
C is a sp
3
-hybridized carbon atom. In certain contexts, the inventive ligand is limited in that when Y is N and Q
1
and Q
2
are combined in a ring structure to form benzene with the backbone of the ligand, then R
5
is not hydrogen. These compounds may be optically active as a result of absolute stereochemical configuration at the sp
3
-hybridized C atom and/or P atom and/or R
3
and/or R
4
substituents.
The ligands characterized by this formula can be included in a composition including a suitable metal or metal precursor compound, 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. The metal-ligand complexes can be characterized by the general formula:
wherein
each R
1
, R
2
, R
3
, R
4
, R
5
, Q
1
, Q
2
, C, X, Y, a and b are as defined above; and
M is a transition metal selected from the group consisting of Groups 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements;
L is independently each occurrence, a neutral and/or charged ligand; and
n is a number 0, 1, 2, 3, 4, and 5, depending on M.
These transition metal-ligand complexes or compositions catalyze reactions involving 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—P, and C—Si bonds. Specifically, such reactions include carbonylation, hydroformylation, hydroxycarbonylation, hydrocarbonylation, hydroesterification, hydrogenation, transfer hydrogenation, hydrosilylation, hydroboration, hydroamination, epoxidation, aziridation, reductive amination, C—H activation, insertion, C—H activation-insertion, C—H activation-substitution, C-halogen activation, C-halogen activation-substitution, C-halogen activation-insertion, cyclopropanation, alkene metathesis, polymerization, alkene oligomerization, alkene polymerization, alkyne oligomerization, alkyne polymerization, co-polymerization, CO-alkene co-oligomerization, CO-alkene co-polymerization, CO-alkyne co-oligomerization and CO-alkyne co-polymerization.
Thus, in one aspect of the invention, new ligands are provided that may be combined with or coordinated to transition metals or precursor compounds to provide useful catalysts.
In another aspect of this invention, new metal-ligand coordination complexes are provided that catalyze chemical reactions, including C—N bond formation.
In yet a further aspect of this invention, a C—N bond formation process is described employing the metal-ligand coordination complexes or compositions of this invention as a or the only component of a catalyst system.
In still a further aspect of this invention, new compounds may be created through the use of the metal-ligand coordination complexes or compositions of this invention as a or the only component of a catalyst system.
Further aspects of this invention will be evident to those of skill in the art upon review of this specification.
DETAILED DESCRIPTION OF THE INVENTION
The invention disclosed herein is a new ligand that may be combined with metals or metal precursor compounds to form coordination complexes or compositions of matter, which are useful as catalysts for chemical reactions.
As used herein, the phrase “characterized by the formula” is not intended to be limiting and is used in the same way that “comprising” is commonly used. The term “independently selected” is used herein to indicate that the R groups, e.g., R
1
, R
2
, R
3
, R
4
, and R
5
can be identical or different (e.g. R
1
, R
2
, R
3
, R
4
, and R
5
may all be substituted alkyls or R
1
and R
2
may be a substituted alkyl and R
3
may be an aryl, etc.). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. For the purposes of illustration,
Nazario-Gonzalez Porfirio
Symyx Technologies Inc.
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