Monocyclopentadienyl complexes

Abstract

Monocyclopentadienyl complexes in which the cyclopentadienyl system bears at least one unsubstantiated, substituted or fused, hetero aromatic ring system bound via a specific bridge, a catalyst system, comprising at least one of these monocyclopentadienyl complexes, the use of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of the catalyst system and polymers obtainable therewith.

1 . A monocyclopentadienyl complex which contains the structural feature of the formula (Cp)(-Z-A) m M (I), where the variables have the following meanings: 
 Cp is a cyclopentadienyl system,    Z is a bridge between A and Cp and is selected from the group consisting of                          where    L 1B -L 3B  are each, independently of one another, carbon or silicon,    R 1B -R 6B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 7B   3 , where the organic radicals R 1B -R 6B  may also be substituted by halogens and two geminal or vicinal radicals R 1B -R 6B  or a radical R 1B -R 6B  and A may also be joined to form a five- or six-membered ring and    R 7B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 7B  may also be joined to form a five- or six-membered ring,    A is an unsubstituted, substituted or fused, heteroaromatic ring system,    M is a metal selected from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten and    m is 1, 2 or 3.    
   
   
       2 . A monocyclopentadienyl complex as claimed in  claim 1  of the formula (Cp)(-Z-A) m MX k  (V), where the variables have the following meanings: 
 Cp is a cyclopentadienyl system,    Z is a bridge between A and Cp and is selected from the group consisting of                          where    L 1B -L 3B  are each, independently of one another, carbon or silicon, R 1B -R 6B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 7B   3 , where the organic radicals R 1B -R 6B  may also be substituted by halogens and two geminal or vicinal radicals R 1B -R 6B  may also be joined to form a five- or six-membered ring and    R 7B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 7B  may also be joined to form a five- or six-membered ring,    A is an unsubstituted, substituted or fused, heteroaromatic ring system,    M is a metal selected from the group consisting of titanium in the oxidation state 3, chromium, molybdenum and tungsten,    m is 1, 2 or 3,    X are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 1 R 2 , OR 1 , SR 1 , SO 3 R 1 , OC(O)R 1 , CN, SCN, β-diketonate, CO, BF 4   − , PF 6   −  or a bulky noncoordinating anion,    R 1 -R 2  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR 3   3 , where the organic radicals R 1 -R 2  may also be substituted by halogens and two radicals R 1 -R 2  may also be joined to form a five- or six-membered ring,    R 3  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 3  may also be joined to form a five- or six-membered ring and    k is 1, 2 or 3.    
   
   
       3 . A monocyclopentadienyl complex as claimed in  claim 1  or  2 , wherein the cyclopentadienyl system Cp has the formula (II):  
     
       
         
         
             
             
         
       
       where the variables have the following meanings:  
       E 1A -E 5A  are each carbon or not more than one E 1A  to E 5A  is phosphorus,  
       R 1A -R 5A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 6A   2 , N(SiR 6A   3 ) 2 , OR 6A , OSiR 6A   3 , SiR 6A   3 , BR 6A   2 , where the organic radicals R 1A -R 5A  may also be substituted by halogens and two vicinal radicals R 1A -R 5A  may also be joined to form a five- or six-membered ring, and/or two vicinal radicals R 1A -R 5A  are joined to form a heterocycle which contains at least one atom from the group consisting of N, P, O and S, and where 1, 2 or 3 substituents R 1A -R 5A  is a group -Z-A and  
       R 6A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two geminal radicals R 6A  may also be joined to form a five- or six-membered ring.  
     
   
   
       4 . A monocyclopentadienyl complex as claimed in any of  claims 1  to  3 , wherein the cyclopentadienyl system Cp together with -Z-A has the formula (IV):  
     
       
         
         
             
             
         
       
       where the variables have the following meanings:  
       E 1A -E 5A  are each carbon or at most one E 1A  to E 5A  is phosphorus,  
       R 1A -R 4A  are each, independently of one another, hydrogen, C 1 -C 20 -allyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 6A   2 ,  
       N(SiR 6A   3 ) 2 , OR 6A , OSiR 6A   3 , SiR 6A   3 , where the organic radicals R 1A -R 4A  may also be substituted by halogens and two vicinal radicals R 1A -R 4A  may also be joined to form a five- or six-membered ring, and/or two vicinal radicals R 1A -R 4A  may be joined to form a heterocycle containing at least one atom from the group consisting of N, P, O and S,  
       R 6A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two geminal radicals R 6A  may also be joined to form a five- or six-membered ring.  
       A is an unsubstituted, substituted or fused, heteroaromatic ring system,  
       Z is a bridge between A and Cp and is selected from the group consisting of  
       
         
           
           
               
               
           
         
       
       where  
       L 1B -L 3B  are each, independently of one another, carbon or silicon,  
       R 1B -R 6B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 7B   3 , where the organic radicals R 1B -R 6B  may also be substituted by halogens and two geminal or vicinal radicals R 1B -R 6B  may also be joined to form a five- or six-membered ring and  
       R 7B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 7B  may also be joined to form a five- or six-membered ring.  
     
   
   
       5 . A monocyclopentadienyl complex as claimed in any of  claims 1  to  4 , wherein A has the formula (IIIa) or (IIIb):  
     
       
         
         
             
             
         
       
       where the variables have the following meanings:  
       E 1C -E 4C  are each carbon or nitrogen,  
       R 1C -R 4C  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 5C   3 , where the organic radicals R 1C -R 4C  may also be substituted by halogens or nitrogen and further C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 5C   3  groups and two vincinal radicals R 1C -R 4C  or R 1C  and Z may also be joined to form a five- or six-membered ring and  
       R 5C  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 5C  may also be joined to form a five- or six-membered ring and  
       p is 0 when E 1C -E 4C  is nitrogen and 1 when E 1C -E 4C  is carbon,  
       G 1C  is nitrogen, phosphorus, sulfur or oxygen,  
       R 6C -R 8C  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 9C   3 , where the organic radicals R 6C -R 8C  may also be substituted by halogens or nitrogen and further C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 9C   3  groups and two vincinal radicals R 6C -R 8C  or R 6C  and Z may also be joined to form a 5- or 6-membered ring and  
       R 9C  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 9C  may also be joined to form a five- or six-membered ring and  
       g is 0 when G 1C  is sulfur or oxygen and 1 when G 1C  is nitrogen or phosphorus.  
     
   
   
       6 . A monocyclopentadienyl complex as claimed in any of  claims 1  to  5 , wherein Z is selected from the group consisting of —C(R 1B R 2B )—Si(R 3B R 4B )—, CH 2 —C(R 3B R 4B )— and 1,2-phenylene.  
   
   
       7 . A catalyst system for olefin polymerization comprising 
 A) at least one monocyclopentadienyl complex as claimed in  claims 1  to  6 ,    B) optionally, an organic or inorganic support,    C) optionally, one or more activating compounds,    D) optionally, further catalysts suitable for olefin polymerization and    E) optionally, one or more metal compounds containing a metal of group 1, 2 or  13  of the Periodic Table.    
   
   
       8 . A prepolymerized catalyst system comprising a catalyst system as claimed in  claim 7  and one or more linear C 2 -C 10 -1-alkenes polymerized onto it in a mass ratio of from 1:0.1 to 1:1 000 based on the catalyst system.  
   
   
       9 . The use of a catalyst system as claimed in  claim 7  or  8  for the polymerization or copolymerization of olefins.  
   
   
       10 . A process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of a catalyst system as claimed in  claim 7  or  8 .  
   
   
       11 . A process for preparing cyclopentadienyl systems of the formula (V):  
     
       
         
         
             
             
         
       
       where the variables have the following meanings:  
       R 1A -R 4A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 6A   2 , N(SiR 6A   3 ) 2 , OR 6A , OSi 6A   3 , SiR 6A   3 , where the organic radicals R 1A -R 4A  may also be substituted by halogens and two vicinal radicals R 1A -R 4A  may also be joined to form a five- or six-membered ring, and/or two vicinal radicals R 1A -R 4A  are joined to form a heterocycle which contains at least one atom from the group consisting of N, P, O and S.  
       R 6A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two geminal radicals R 6A  may also be joined to form a five- or six-membered ring,  
       A is an unsubstituted, substituted or fused, heteroaromatic ring system,  
       R 1B -R 4B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 7B   3 , where the organic radicals R 1B -R 4B  may also be substituted by halogens and two geminal vicinal radicals R 1B -R 4B  may also be joined to form a five- or six-membered ring and  
       R 7B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 7B  may also be joined to form a five- or six-membered ring,  
       M S  a metal of group 1, 2 or 3 of the Periodic Table of the Elements,  
       X S  are each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, alkylaryl having 1-10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 1 R 2 , OR 1 , SR 1 , SO 3 R 1 , OC(O)R 1 , CN, SCN, β-diketonate, CO, BF 4   − , PF 6   −  or a bulky noncoordinating anion and  
       s 0, 1 or 2,  
       r 1 or 2, with the proviso that s+r is the oxidation state of M S −1, which comprises reacting (A-CR 1B R 2B   − ) r (M S X S   S ) +  with a fulvene of the formula (VI)  
       
         
           
           
               
               
           
         
       
     
   
   
       12 . A process for preparing cyclopentadienyl systems of the formula (VIII):  
     
       
         
         
             
             
         
       
       where the variables have the following meanings:  
       E 6A -E 10A  are each carbon or not more than one E 6A  to E 10A  is phosphorus, where four adjacent E 6A -E 10A  form a conjugated diene system and the remaining E 6A -E 10A  additionally bears a hydrogen atom,  
       R 1A -R 4A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR 6A   2 , N(SiR 6A   3 ) 2 , OR 6A , OSiR 6A   3 , SiR 6A   3 , where the organic radicals R 1A -R 4A  may also be substituted by halogens and two vicinal radicals R 1A -R 4A  may also be joined to form a five- or six-membered ring, and/or two vicinal radicals R 1A -R 4A  are joined to form a heterocycle which contains at least one atom from the group consisting of N, P, O and S,  
       R 6A  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two geminal radicals R 6A  may also be joined to form a five- or six-membered ring,  
       A is an unsubstituted, substituted or fused, heteroaromatic ring system,  
       R 1B -R 4B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR 7B   3 , where the organic radicals R 1B -R 4B  may also be substituted by halogens and two geminal or vicinal radicals R 1B -R 4B  may also be joined to form a five- or six-membered ring, and  
       R 7B  are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R 7B  may also be joined to form a five- or six-membered ring,  
       which comprises reacting (A-CR 1B R 2B− ) r (M S X S   S ) +  with a cyclopentadienyl system of the formula (IX)  
       
         
           
           
               
               
           
         
       
       where the variables are as defined above and  
       Q is a leaving group.