Compositions and metal complexes having ancillary ligands

Details Compositions and metal complexes having ancillary ligands Compositions and metal complexes having ancillary ligands

1998-07-20

2001-06-05

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S019000, C556S057000, C556S146000, C556S150000, C526S160000, C526S943000, C502S104000, C502S150000

Reexamination Certificate

active

06242623

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to compositions and metal complexes that are useful as catalysts and in particular olefin polymerization catalysts.
BACKGROUND OF THE INVENTION
Ancillary ligand stabilized metal complexes (e.g., organometallic complexes) are useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents and drugs. The ancillary ligand system comprises organic substituents that bind to the metal center(s), remain associated with the metal center(s), and therefore provide an opportunity to modify the shape, electronic and chemical properties of the active metal center(s) of the organometallic complex.
Certain organometallic complexes are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilylation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions and other transformations. Organometallic complexes can be prepared by combining an ancillary ligand precursor with a suitable metal precursor in a suitable solvent at a suitable temperature.
One example of the use of organometallic complexes is in the field of single-sited olefin polymerization catalysis. The active site typically comprises an ancillary ligand-stabilized, coordinatively unsaturated transition metal alkyl complex.
It is always a desire to discover new catalysts and catalyst systems that may catalyze reactions differently from known ligand systems. This invention provides new compositions, metal compounds and catalyst systems.
SUMMARY OF THE INVENTION
In one aspect, this invention relates to ancillary ligands that are combined with metal precursors to form an active catalyst composition. The ancillary ligands can be described by the general formula:
where E
1
and E
2
are elements, each of which is, independently, selected from the group consisting of N, P, O, S and Se;
Z is an element or molecule selected from the group consisting of H, Li, TMS, SnBu
3
, Na, K, Rb, Ti, Ag and MgT, where T is a halogen (F, Cl, Br and I);
R
1
and R
3
are groups that may be independently selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl;
R
2
is a group that may be selected from the group consisting of hydrocarbyl, alkoxides, aryloxides (—OX), thioethers, (—SX) phosphines (—PX
2
), arsines (—AsX
2
), silanes (—SiX
3
), germanes (—GeX
3
), amides (—NX
2
) and combinations thereof. In each of these formulas, X is selected from the group consisting of alkyls, aryls, substituted alkyls and substituted aryls and combinations thereof.
In this first aspect, the ancillary ligand is combined with a metal precursor to form a composition. The metal precursors can be described by the general formula:
R′
a
ML
b
T
c
where M is a metal selected from Groups 2-12 of the Periodic Table of Elements;
R′ is a group that forms a bond with M such that an olefin, diolefin or acetylenically unsaturated monomer or a functionalized version thereof (such as a functionalized olefin) can insert into the bond between R′ and M. R′ is typically selected from the group consisting of hydrocarbyl, silyl, germyl and hydride; a is 1, 2, 3 or 4 depending on the oxidation state of M.
L is an optional ligand, which, when present is a dative ligand (including agostic interactions), which can be selected from the group consisting of olefins, functionalized olefins, ethers, pyridines, nitriles, thioethers, phosphines, amines carbonyls and combinations thereof; and b is 0, 1, 2, 3 or 4.
T is a halogen and c is 0, 1 or 2. The halogen is present in certain embodiments.
In another aspect, this invention relates to compounds, which can be described by the general formula:
or a dimer, trimer or higher aggregate thereof,
wherein M is a metal selected from Groups 7-12 of the Periodic Table of Elements;
E
1
and E
2
are elements, each of which is, independently, selected from the group consisting of N, P, O, S and Se;
R′ is a group that forms a bond with M such that an olefin, diolefin or acetylenically unsaturated monomer or a functionalized version thereof (such as a functionalized olefin) can insert into the bond between R′ and M. R′ is typically selected from the group consisting of hydrocarbyl, silyl, germyl and hydride.
L is an optional ligand, which, when present is a dative ligand (including agostic interactions), which can be selected from the group consisting of olefins, functionalized olefins, ethers, pyridines, nitriles, thioethers, phosphines, amines, carbonyls and combinations thereof.
R
1
and R
3
are groups that may be independently selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl;
R
2
is a group that may be selected from the group consisting of hydrocarbyl, alkoxides, aryloxides (—OX), thioethers, (—SX) phosphines (—PX
2
), arsines (—AsX
2
), silanes (—SiX
3
), germanes (—GeX
3
), amides (—NX
2
) and combinations thereof. In each of these formulas, X is selected from the group consisting of alkyls, aryls, substituted alkyls and substituted aryls and combinations thereof. Additionally R
2
may bind further to the metal via a dative bond from one of the above group of molecules or through a functionality, Q, which can be depicted by the general formula:
where Q is a functionality having a lone pair of electrons capable of dative binding to the metal. Generally, Q is a molecule including an atom selected from the group consisting of N, O, S, P and halogens (Cl, Br, I and F). When the functionality Q is present, M may be selected from the group consisting of Groups 2-12 of the Periodic Table of Elements. Also when Q is present, R
2
is generally a combination of the groups listed above, such that Q may be selected from the group consisting of heteroarylalkyls, substituted heteroarylalkyls, heterocyclicalkyls, substituted heterocyclicalkyls, alkylarines arylamines and the like.
Optionally, R
2
may further bind to the metal via two dative bonds from the group of molecules listed above or through the functionalities Q
1
and Q
2
, where Q
1
and Q
2
may be the same or different, but each has the same definition as Q, above. This can be depicted by the general formula:
Alternatively, R
2
may bind further to the metal via a covalent bond such as depicted by the general formula:
where Y is a functionality capable of covalently bonding to the metal. Generally Y is a molecule including an atom selected from the group consisting of N, O, S and P. Suitable groups are amides, phosphides, aryloxides, alkoxides, thiols and the like. When Y is present M may be selected from the group consisting of Groups 3-10 of the Periodic Table of Elements. Y is generally a combination of the groups listed above for R
2
. For example, Y may be selected from the group consisting of heteroarylalkyls, substituted heteroarylalkyls, heterocyclicalkyls, substituted heterocyclicalkyls, alkylamines, arylamines and the like.
Additionally R
2
may bind further to the metal via two a covalent bonds from functionalities Y
1
and Y
2
, where Y
1
and Y
2
may be the same or different, but each has the same definition as Y, above. Such a complex may be depicted by the general formula:
When both Y
1
and Y
2
are present, M may be selected from the group consisting of Groups 4-10 of the Periodic Table of Elements.
Optionally, R
2
may bind further to the metal via one covalent bond, and one dative bond such as depicted by the general formula:
where Y and Q are as defined above and M can be selected from the group consisting of Groups 3-10 of the Periodic Table of Elements.
The complexes of this invention are suitable as catalysts for the polymerization of olefins. They may be used with or without an activator. Monomers that may be polymerized by the complexes of this invention are: olefins, diolefins and acetylenically unsaturated monomers, as well as functionalized versio

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