Monocyclopentadienyl complexes

1. A monocyclopentadienyl complex comprising a structural feature of formula Cp-Y m M A (I), wherein:

Cp is a cyclopentadienyl system comprising an aryl substituent;

Y is a substituent which is bound to Cp and comprising at least one uncharged donor comprising at least one atom of group 15 or 16 of the Periodic Table;

M A is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, or an element of group 3 or a lanthanide of the Periodic Table; and

m is 1, 2 or 3.

2. A monocyclopentadienyl complex comprising formula Cp-Y m M A X A n (V), wherein:

Cp is a cyclopentadienyl system comprising an aryl substituent;

Y is a substituent which is bound to Cp and comprises at least one uncharged donor comprising at least one atom of group 15 or 16 of the Periodic Table;

M A is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, or an element of group 3 or a lanthanide of the Periodic Table;

m is 1, 2 or 3;

X A independently of one another, are fluorine, chlorine, bromine, iodine, hydrogen, a C 1 -C 10 -alkyl, a C 2 -C 10 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 23A R 24A , OR 23A , SR 23A , SO 3 R 23A , OC(O)R 23A , CN, SCN, β-diketonate, CO, BF 4 − , PF 6 − or bulky noncoordinating anions, or two radicals X A form a substituted or unsubstituted diene ligand, or two or more X A radicals may be joined to one another;

R 23A -R 24A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 25A 3 , wherein R 23A -R 24A may also be substituted by halogens or nitrogen- and oxygen-containing groups, or two R 23A -R 24A radicals optionally can be joined to form a five- or six-membered ring;

R 25A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein two R 25A radicals optionally can join to form a five- or six-membered ring; and

n is 1, 2, or 3.

3. The monocyclopentadienyl complex as claimed in claim 2 , wherein X A is a 1,3-diene ligand.

4. The monocyclopentadienyl complex as claimed in claim 1 , wherein Y comprises group -Z k -A-; the group -Z k -A- together with the cyclopentadienyl system Cp and M A form a monocyclopentadienyl complex comprising formula Cp-Z k -A-M A (II), wherein CP-Z k -A comprises:

wherein:

E 1A -E 5A are each carbon or a heteroatom, with the proviso that not more than one E 1A -E 5A are phosphorus;

R 1A -R 4A independently of one another, are hydrogen, a C 1 -C 22 -alkyl, a C 2 -C 22 -alkenyl, a C 6 -C 22 -aryl, an alkylaryl comprising 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 5A 2 , N(SiR 5A 3 ) 2 , OR 5A , OSiR 5A 3 , SiR 5A 3 , BR 5A 2 , wherein optionally R 1A -R 4A can be substituted by at least one halogen, or two vicinal R 1A -R 4A radicals optionally can be joined to form a five-, six-, or seven-membered ring, or two vicinal R 1A -R 4A radicals optionally can be joined to form a five-, six-, or seven-membered heterocycle ring comprising at least one atom from the group consisting of N, P, O and S, with the proviso that at least one R 1A -R 4A is a C 1 -C 22 -alkyl, a C 2 -C 22 -alkenyl, a halogen, a haloalkyl comprising 1-10 carbon atoms, or a haloaryl comprising 1-10 carbon atoms, or a C 6 -C 22 aryl, wherein the C 6 -C 22 aryl optionally can be substituted by N—, P—, O— or S-containing substituents;

R 5A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or two geminal radicals that optionally can be joined to form a five- or six-membered ring;

Z is a divalent bridge between A and Cp selected from the group consisting of:

—BR 6A —, —BNR 6A R 7A —, AlR 6A —, —Sn—, —O—, —S—, —SO—, —SO 2 —, —NR 6A —, —CO—, —PR 6A — or —P(O)R 6A ,

wherein

L 1A -L 3A independently of one another, are silicon or germanium;

R 6A -R 11A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 12 A 3 , wherein R 6A -R 11A optionally can be substituted by at least one halogen or two geminal or vicinal R 6A -R 11A radicals optionally can be joined to form a five- or six-membered ring;

R 12A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, a C 6 -C 20 alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, a C 1 -C 10 -alkoxy, or C 6 -C 10 -aryloxy, wherein two R 12A radicals optionally can be joined to form a five- or six-membered ring;

A is an uncharged donor group comprising at least one atom of group 15 or 16 of the Periodic Table of Elements, or a carbine;

M A is a metal selected from the group consisting of titanium comprising an oxidation state 3, vanadium, chromium, molybdenum, and tungsten; and

k is 0 or 1.

5. The monocyclopentadienyl complex as claimed in claim 4 , wherein A is an unsubstituted, substituted, or fused heteroaromatic ring system.

6. The monocyclopentadienyl complex as claimed in claim 2 , wherein Y comprises group -Z k -A-; the group -Z k -A together with the cyclopentadienyl system Cp, and M A forms a monocyclopentadienyl complex comprising formula Cp-Z k -A-M A (II), wherein CP-Z k -A comprises:

wherein:

E 1A -E 5A are each carbon or a heteroatom, with the proviso that not more than one E 1A -E 5A are phosphorus;

R 1A -R 4A independently of one another, are hydrogen, a C 1 -C 22 -alkyl, a C 2 -C 22 -alkenyl, a C 6 -C 22 -aryl, an alkylaryl comprising 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 5A 2 , N(SiR 5A 3 ) 2 , OR 5A , OSiR 5A 3 , SiR 5A 3 , BR 5A 2 , wherein optionally R 1A -R 4A can be substituted by at least one halogen, or two vicinal R 1A -R 4A radicals optionally can be joined to form a five-, six-, or seven-membered ring, or two vicinal R 1A -R 4A radicals optionally can be joined to form a five-, six-, or seven-membered heterocycle ring comprising at least one atom from the group consisting of N, P, O and S, with the proviso that at least one R 1A -R 4A is a C 1 -C 22 -alkyl, a C 2 -C 22 -alkenyl, a halogen, a haloalkyl comprising 1-10 carbon atoms, or a haloaryl comprising 1-10 carbon atoms, or a C 6 -C 22 aryl, wherein the C 6 -C 22 aryl optionally can be substituted by N—, P—, O— or S-containing substituents;

R 5A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or two geminal radicals that optionally can be joined to form a five- or six-membered ring;

Z is a divalent bridge between A and Cp selected from the group consisting of:

—BR 6A —, —BNR 6A R 7A —, —AlR 6A —, —Sn—, —O—, —S—, —SO—, —SO 2 —, —NR 6A —, —CO—, —PR 6A — or —P(O)R 6A ,

wherein

L 1A -L 3A independently of one another, are silicon or germanium;

R 6A -R 11A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 12A 3 , wherein R 6A -R 11A optionally can be substituted by at least one halogen or two geminal or vicinal R 6A -R 11A radicals optionally can be joined to form a five- or six-membered ring;

R 12A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, a C 6 -C 20 alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, a C 1 -C 10 -alkoxy, or C 6 -C 10 -aryloxy, wherein two R 12A radicals optionally can be joined to form a five- or six-membered ring;

A is an uncharged donor group comprising at least one atom of group 15 or 16 of the Periodic Table of Elements, or a carbine;

M A is a metal selected from the group consisting of titanium comprising an oxidation state 3, vanadium, chromium, molybdenum, and tungsten; and

k is 0 or 1.

7. The monocyclopentadienyl complex as claimed in claim 6 , wherein A is an unsubstituted, substituted, or fused heteroaromatic ring system.

8. The monocyclopentadienyl complex as claimed in claim 4 , wherein A comprises formula (IVa) or (IVb):

wherein:

E 6A -E 11A independently of one another, are carbon or nitrogen;

R 16A -R 21A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 22A 3 , wherein R 16A -R 21A optionally can be substituted by at least one halogen or nitrogen, or two vicinal R 16A -R 21A radicals or R 16A and Z optionally can be joined to form a five- or six-membered ring;

R 22A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -a C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or two R 22A radicals optionally can be joined to form a five- or six-membered ring; with the proviso that

p is 0 when E 6A -E 11A is nitrogen, and p is 1 when E 6A -E 11A is carbon.

9. The monocyclopentadienyl complex as claimed in claim 5 , wherein A comprises formula (IVa) or (IVb):

wherein:

E 6A -E 11A independently of one another, are carbon or nitrogen;

R 16A -R 21A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 22A 3 , wherein R 16A -R 21A optionally can be substituted by at least one halogen or nitrogen, or two vicinal R 16A -R 21A radicals or R 16A and Z optionally can be joined to form a five- or six-membered ring;

R 22A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -a C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or two R 22A radicals optionally can be joined to form a five- or six-membered ring; with the proviso that

p is 0 when E 6A -E 11A is nitrogen, and p is 1 when E 6A -E 11A is carbon.

10. The monocyclopentadienyl complex as claimed in claim 4 , wherein -Z-A and the aryl substituent are in the 1,3-positions relative to one another.

11. The monocyclopentadienyl complex as claimed in claim 6 , wherein -Z-A and the aryl substituent are in the 1,3-positions relative to one another.

12. A catalyst system for olefin polymerization comprising:

A) at least one monocyclopentadienyl complex according to claim 1 ;

B) optionally, an organic or inorganic support;

C) optionally, one or more activating compounds;

D) optionally, further catalysts for olefin polymerization; and

E) optionally, one or more metal compounds comprising a metal of group 1, 2 or 13 of the Periodic Table.

13. The prepolymerized catalyst system comprising a catalyst system as claimed in claim 12 , the catalyst system further comprising one or more linear C 2 -C 10 1-alkenes polymerized onto the catalyst system in a mass ratio of from 1:0.1 to 1:1,000.

14. The process for preparing polyolefins by polymerization or copolymerization of olefins in presence of the catalyst system as claimed in claim 12 .

15. The process for preparing polyolefins by polymerization or copolymerization of olefins in presence of the catalyst system as claimed in claim 13 .

16. A process for preparing a cyclopentadiene system of formula (VIa)

wherein

E 12A -E 16A are each carbon, wherein four adjacent E 12A -E 16A form a conjugated diene system and the remaining E 12A -E 16A bears hydrogen,

R 26A -R 29A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, a C 6 -C 20 alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 32A 2 , N(SiR 32A 3 ) 2 , OR 32A , OSiR 32A 3 , BR 32A 2 , SiR 32A 3 , wherein R 26A -R 29A optionally can be substituted by at least one halogen or two vicinal R 26A -R 29A radicals that optionally can be joined to form a five- or six-membered ring, or two vicinal R 26A -R 29A radicals optionally can form a heterocycle comprising at least one atom from the group consisting of N, P, O or S;

R 30A -R 31A independently of one another, are a hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, a alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, or SiR 32A 3 , wherein R 30A -R 31A optionally can be substituted by at least one halogen, and R 30A and A, or R 31A and A optionally can be joined to form a five- or six-membered ring;

R 32A independently of one another, are hydrogen, a C 1 -C 20 -alkyl, a C 2 -C 20 -alkenyl, a C 6 -C 20 -aryl, an alkylaryl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, and two geminal R 32A radicals optionally can be joined to form a five- or six-membered ring;

m is 0, 1 or 2;

A is an uncharged donor group comprising at least one atom of group 15 or 16 of the Periodic Table of Elements, or a carbine;

the process comprising:

reacting an (A-(CR 29A R 30A ) m ) − anion with a cyclopentanedione or a silyl ether of an enolised cyclopentanedione.

17. The process of claim 16 , wherein A is an unsubstituted, substituted, or fused heteroaromatic ring system.