Catalysts based on metal fulvene complexes

Details Catalysts based on metal fulvene complexes Catalysts based on metal fulvene complexes

1999-08-13

2001-04-10

Bell, Mark L. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S150000, C502S151000, C502S154000, C502S162000, C502S167000, C502S172000, C526S160000, C526S161000, C526S172000, C526S943000

Reexamination Certificate

active

06214762

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to catalysts based on metal fulvene complexes, to methods of producing them, and to the use thereof for the polymerization and copolymerization of olefins and/or dienes.
BACKGROUND OF THE INVENTION
Since the discovery of ferrocene, metal complexes with cyclopentadienyl ligands have been intensively investigated. The use of biscyclopentadienyl-metal complexes (metallocenes), in admixture with activating co-catalysts, preferably alumoxanes, for the polymerization of olefins and diolefins has long been known (e.g., EP-A 69,951, 129,368, 351,392, 485,821, 485,823). Metallocenes have proven to be highly effective, specific catalysts for the polymerization of olefins. In combination with co-catalysts, metal complexes with only one cyclopentadienyl ligand (semi-sandwich complexes) are also suitable as specific polymerization catalysts (US. Pat. No. 5,132,380, EP 416,815, WO 91/04257, WO 96/13529). There is, therefore, a multiplicity of new metallocene catalysts or semi-sandwich catalysts for the polymerization of olefinic compounds which have been developed in recent years in order to increase catalyst activity and selectivity and to control the microstructure, molecular weights and molecular weight distribution thereof. Metal complexes with cyclopentadienyl ligands, particularly chiral ansa-metallocenes, have also been described as hydrogenation catalysts, e.g., for olefins or imines (J. Am. Chem. Soc. 1993, 115, 12569. J. Am. Chem. Soc. 1994, 116, 8952-8965). Chiral metallocenes are also used as catalysts in asymmetric synthesis, e.g. for asymmetric Diels-Alder reactions (J. Chem. Soc. Chem. Commun. 1995, 1181).
However, relatively little is known about metal complexes with fulvene ligands. According to Bercaw et al., JACS (1972), 94, 1219, the fulvene complex (&eegr;
6
-2,3,4,5-tetra-methylcyclopentadienyl-1-methylene)(&eegr;
5
-pentamethylcyclo-pentadienyl)-titanium-methyl is formed by the thermolysis of bis(&eegr;
5
-pentamethylcyclo-penta-dienyl)-titaniumdimethyl.
T. J. Marks et al., JACS (1988), 110, 7701 describes the thermolysis of pentamethylcyclopentadienyl complexes of zirconium and hafnium. The fulvene complex (&eegr;
6
-2,3,4,5-tetramethylcyclopentadienyl-1-meth-ylene)(&eegr;
5
-penta-methylcyclopentadienyl)zirconiumphenyl is formed by the thermolysis of bis(&eegr;
5
-pentamethylcyclopentadienyl)zirconiumdiphenyl. The production of fulvene complexes by a thermal method is restricted to just a few structural variants. The thermal method does not always result in uniform products.
Metal fulvene complexes and a method of producing them were described in a previous Application (German Patent Application 19 756 742.8). Metal fulvene complexes which cannot be obtained by a thermal method can be obtained in high yield by the reaction of a fulvene compound with a suitable transition metal complex in the presence of a reducing agent. The direct introduction of the fulvene ligand provides access to a multiplicity of fulvene metal complexes. In combination with co-catalysts, specific polymerization catalysts can be produced, the catalytic activity of which is comparable with the activity of catalysts based on metallocenes.
A method of producing metal fulvene complexes by a thermal route, and their use as polymerization catalysts in combination with co-catalysts, is described in the prior Application DE 19 732 804.0.
One disadvantage is that metal fulvene complexes are extremely sensitive to air and moisture. Metal fulvene complexes, therefore, have to be produced and stored under inert gas conditions.
Little is known about the reaction behavior of metal fulvene complexes. The reaction of aldehydes and ketones with the complex compound (&eegr;
6
-cyclopentadienyl-1-methylene)(&eegr;
5
-methylcyclopentadienyl)phenyltitanium is described in Z. Natur-forsch. 44 b, 1989, 1593-1598. The reaction of isonitriles with pentamethylcyclopentadienyltetramethylfulvene complexes of titanium and zirconium is described in Organometallics 1991, 10, 2665-2671. The reaction of (&eegr;
6
-2,3,4,5-tetramethylcyclo-pentadienyl-1-methylene)(&eegr;
5
-pentamethylcyclopentadienyl)titanium chloride with acetophenone is described in Organometallics, 1991, 10, 1637-1639. The reaction products which are formed have not been characterized unambiguously. The reactions described above are restricted to metal fulvene complexes which comprise a cyclopentadienyl ligand in addition and which are produced by a thermal method.
SUMMARY OF THE INVENTION
Nothing is known about the reaction behavior of metal fulvene complexes which are produced by the direct introduction of a fulvene ligand into a metal complex.
The object of the present invention is to identify new catalysts which, at least in part, avoid the disadvantages described above.
Surprisingly, it has been found that new metal fulvene insertion complexes which are superbly suitable as catalysts can be produced by the reaction of metal fulvene complexes with unsaturated compounds which contain one or more hetero atoms.
The present invention relates to a method of producing metal fulvene insertion complexes comprising the step of reacting
a) a metal fulvene complex of formula (I)
 wherein
M is a metal of Groups IIIb, IVb, Vb, VIb or of the lanthanides or of the actinides of the IUPAC periodic table of the elements,
A is an anionic ligand which is optionally singly- or multi-bridged, with the exception of cyclopentadienyl ligands,
X denotes a hydrogen atom, a C
1
to C
10
alkyl group, a C
1
to C
10
alkoxy group, a C
6
to C
10
aryl group, a C
6
to C
10
aryloxy group, a C
2
to C
10
alkenyl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a C
8
to C
40
arylalkenyl group, a silyl group substituted by C
1
to C
10
hydrocarbon radicals, a halogen atom or an amide of formula NR
7
2
,
L denotes a neutral ligand,
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
are the same or different and represent hydrogen, a halogen, a cyano group, a C
1
to C
20
alkyl group, a C
1
to C
10
fluoro-alkyl group, a C
6
to C
10
fluoroaryl group, a C
1
to C
10
alkoxy group, a C
6
to C
20
aryl group, a C
6
to C
10
aryloxy group, a C
2
to C
10
alkenyl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a C
7
to C
40
arylalkenyl group, a C
2
to C
10
alkynyl group, a silyl group substituted by C
1
-C
10
hydrocarbon radicals, a sulfide group substituted by a C
1
-C
10
hydrocarbon radical, or an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals, or
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
each form one or more aliphatic or aromatic ring systems together with the atoms which bond them, which ring systems may contain one or more hetero atoms (O, N, S) and comprise 5 to 10 carbon atoms,
R
7
represents hydrogen, a C
1
to C
20
alkyl group, a C
6
to C
20
aryl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a silyl group which is substituted by C
1
-C
10
hydrocarbon radicals, or an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals,
m, p represent the numbers 0, 1, 2, 3 or 4 which result from the valency and the state of bonding of M,
k represents the number 1, 2 or 3, and the sum of k+m+p ranges from 1 to 5 depending on the oxidation state of M, and
n is a number from 0 to 10,
 with
b) an unsaturated compound of formula (II)
R
8
a
R
9
b
CY  (II),
 wherein
R
8
and R
9
are the same or different, and denote a hydrogen atom, a halogen atom, a hydroxy group, a C
1
to C
10
alkyl group, a C
1
to C
10
alkoxy group, a C
6
to C
10
aryl group which is optionally substituted by halogen atoms, a C
6
to C
10
aryloxy group, a C
2
to C
10
alkenyl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a C
8
to C
40
arylalkenyl group, an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals, or an imino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals,
Y denotes a nitrogen atom, an oxygen atom, a sulphur atom or a

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