Meso-selective synthesis of ansa-metallocenes
View Patent ↗The present invention relates to a process for the meso-selective preparation of ansa-metallocene complexes of the formula (I), which comprises reacting a ligand starting compound of the formula (II) with a transition metal compound of the formula III, where R 1 , R 1 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R 2 , R 2 are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms, R 3 is a bulky organic radical which has at least 3 carbon atoms, is bound to the oxygen atom via a nonaromatic carbon or silicon atom and may be substituted by halogen atoms or further organic radicals having from 1 to 20 carbon atoms and may also contain heteroatoms selected from the group consisting of Si, N, P, O and S, T, T′ are identical or different and are each a divalent organic group which has from 1 to 40 carbon atoms and together with the cyclopentadienyl ring forms at least one further saturated or unsaturated, substituted or unsubstituted ring system having a ring size of from 5 to 12 atoms, where T and T′ may contain the heteroatoms Si, Ge, N, P, As, Sb, O, S, Se or Te within the ring system fused to the cyclopentadienyl ring, A is a bridge consisting of a divalent atom or a divalent group, M 1 is an element of group 3, 4, 5 or 6 of the Periodic Table of the Elements or the lanthanides, the radicals X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion, x is a natural number from 1 to 4, M 2 is an alkali metal, an alkaline earth metal or a magnesium monohalide fragment, p is 1 in the case of doubly positively charged metal ions or 2 in the case of singly positively charged metal ions or metal ion fragments, LB is an uncharged Lewis base ligand, and y is a natural number from 0 to 6, and also the subsequent reaction of these complexes to form ansa-metallocenes of the formula (IV), the use of transition metal compounds of the formula (III) for preparing metallocenes and also transition metal compounds of the formula (III), ansa-metallocene complexes of the formula (I) and the use of these as constituents of catalyst systems for the polymerization of olefines.
1. A process for meso-selective preparation of ansa-metallocene complexes of formula (I):
which comprises reacting a ligand starting compound of formula (II):
with a transition metal compound of formula (III):
(LB) y M 1 (OR 3 )X x+1 (III)
where
R 1 , R 1′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 2 , R 2′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 3 is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S;
T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
M 1 is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements;
X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion;
x is a natural number from 1 to 4;
M 2 is an alkali metal, an alkaline earth metal, or a magnesium monohalide fragment;
p is 1 when M 2 is a doubly positively charged metal ion, or 2 when M 2 is a singly positively charged metal ion or metal ion fragment;
LB is an uncharged Lewis base ligand;
and
y is a natural number from 0 to 6.
2. The process as claimed in claim 1 , wherein an ansa-metallocene complex of formula (I) is converted into an ansa-metallocene complex of formula (IV):
where
R 1 , R 1′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 2 , R 2′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
M 1 is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements;
X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and
x is a natural number from 1 to 4;
comprising reacting the ansa-metallocene complexes of formula (I) with at least one suitable elimination reagent in a subsequent reaction step.
3. The process as claimed in claim 1 , wherein
R 1 , R 1′ are identical or different and are each a C 1 -C 10 -alkyl;
R 2 , R 2′ are each hydrogen;
T, T′ are identical or different and are each an unsubstituted 1,3-butadiene-1,4-diyl group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to 4 R 4 radicals, where R 4 can be identical or different and are organic radicals having from 1 to 40 carbon atoms; and
A is ethylene, substituted ethylene or substituted silylene.
4. The process as claimed in claim 2 , wherein
R 1 , R 1′ are identical or different and are each a C 1 -C 10 -alkyl;
R 2 , R 2′ are each hydrogen;
T, T′ are identical or different and are each an unsubstituted 1,3-butadiene-1,4-diyl group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to 4 R 4 radicals, where R 4 can be identical or different and are organic radicals having from 1 to 40 carbon atoms; and
A is ethylene, substituted ethylene or substituted silylene.
5. The process as claimed in claim 1 , wherein
R 3 is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms;
M 1 is Ti, Zr or Hf;
X is halogen;
x is 2;
LB is a cyclic or acyclic ether or diether;
and
y is 1 or 2.
6. The process as claimed in claim 2 , wherein
R 3 is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms;
M 1 is Ti, Zr or Hf;
X is halogen;
x is 2;
LB is a cyclic or acyclic ether or diether;
and
y is 1 or 2.
7. The process as claimed in claim 1 , wherein
M 2 is Li, Na, K, MgCl, MgBr, MgI or Mg.
8. The process as claimed in claim 2 , wherein
M 2 is Li, Na, K, MgCl, MgBr, MgI or Mg.
9. A method for preparing ansa-metallocene complexes comprising reacting a metallocene complex with a transition metal compound of formula (III):
(LB) y M 1 (OR 3 )X X+1 (III).
10. A transition metal compound of the formula (III):
(LB) y M 1 (OR 3 )X X+1 (III)
where
R 3 is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S;
M 1 is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements;
X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion;
x is a natural number from 1 to 4;
LB is an uncharged Lewis base ligand;
and
y is a natural number from 0 to 6.
11. A method for preparing ansa-metallocene complexes of formula (IV) as set forth in claim 2 comprising reacting a metallocene complex of formula (I):
where
R 1 , R 1′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 2 , R 2′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 3 is a bulky organic radical comprising at least 3 carbon atoms, and is bound to the oxygen atom via a nonaromatic carbon or silicon atom, and may be substituted by halogen atoms or further organic radicals comprising from 1 to 20 carbon atoms, and optionally comprise at least one heteroatom selected from the group consisting of Si, N, P, O and S;
T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
M 1 is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements;
X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and
x is a natural number from 1 to 4;
with a transition metal compound.
12. An ansa-metallocene complex of formula (I):
where
R 1 , R 1′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 2 , R 2′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
R 3 is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms;
M 1 is Ti, Zr or Hf;
X is halogen; and
x is 2.
13. A constituent of a catalyst system for polymerizing at least one olefin comprising an ansa-metallocene complex of formula (I):
R 1 , R 1′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 2 , R 2′ are identical or different and are each hydrogen or an organic radical having from 1 to 40 carbon atoms;
R 3 is an alkyl radical branched in an α position, and comprises from 4 to 40 carbon atoms, and is optionally substituted by at least one halogen atom or organic radical comprising from 1 to 10 carbon atoms;
T, T′ are identical or different and are each a divalent organic group comprising from 1 to 40 carbon atoms, and together with the cyclopentadienyl rings form at least one further saturated or unsaturated, substituted or unsubstituted ring system comprising from 5 to 12 atoms, where T and T′ optionally comprises at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
M 1 is at least one lanthanide or an element of group 3, 4, 5 or 6 of the Periodic Table of Elements;
X are identical or different and are each an organic or inorganic radical which is able to be replaced by a cyclopentadienyl anion; and
x is a natural number from 1 to 4.