Metallocene complexes, their synthesis and use in catalyst systems for olefin polymerization

A metallocene complex represented by the formula I, II, III, or IV:

• where M is a metal selected from Group 4, 5, 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements (the formulae above are represented as a four coordinate metal, in the event the metal has a coordination number of 3, then one X group is missing, if the metal has a coordination number of 5 or 6 then one or two more X groups are present, respectively);
• T is a bridging group;
• X is a univalent anionic ligand;
• Z is a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, or a heteroatom containing group;
• R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, and R23 are, independently selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbyl, halohydrocarbyl, silylhydrocarbyl or silylhalohydrocarbyl groups, wherein two adjacent R substituents may form all or part of a saturated, partially unsaturated or aromatic monocyclic or polycyclic ring structure, provided that at least one of R1, R2, R3, or R4 in formula I, at least one of R5, R6, R7, R8, R9, or R10 in formula II, at least one of R11, R12, R13, R14, R15, R16, R17, or R18 in formula III, or at least one of R19, R20, R21, R22, or R23 in formula IV is an Si—N group represented by the formula:
• where R24, R25, R26 and R27 are, independently, substituted or unsubstituted hydrocarbyl groups, where at least one of R26 and R27 has at least 2 carbon aroms, and/or where two adjacent R24, R25, R26 and R27 substituents may be joined to form part of a monocyclic or polycyclic ring structure.

An olefin polymerization catalyst system comprising:

• (a) a metallocene complex represented by the formula
• (CpR5)nMXk
• where Cp (each occurrence) is a cyclopentadienyl group;
• each of the five R substituents on the or each cyclopentadienyl group is independently selected from hydrogen, C1, to C30 substituted or unsubstituted hydrocarbyl, halohydrocarbyl, silylhydrocarbyl or silylhalohydrocarbyl, wherein two adjacent R substituents may be joined to form part of a saturated, partially unsaturated or aromatic monocyclic or polycyclic ring structure, and SiR′2NR″2 where each of the two R′ substituents is independently selected from C1, to C30 substituted or unsubstituted hydrocarbyl, halohydrocarbyl, silylhydrocarbyl or silylhalohydrocarbyl, wherein two adjacent R′ substituents may be joined to form part of a saturated, partially unsaturated or aromatic monocyclic or polycyclic ring structure, and each of the two R″ substituents is independently selected from C2 to C30 substituted or unsubstituted hydrocarbyl, halohydrocarbyl, silylhydrocarbyl or silylhalohydrocarbyl, wherein two adjacent R″ substituents may be joined to form part of a saturated, partially unsaturated or aromatic monocyclic or polycyclic ring structure, and where a R′ and a R″ may join together to form part of a monocyclic or polycyclic ring structure;
• n is 1 or 2;
• M is a transition metal of valence m from Groups 4 to 11 of the Periodic Table of Elements,
• k is equal to m minus n;
• and
• the or each X substituent is a univalent anionic ligand, or two X substituents are joined and bound to the metal atom to form a metallocycle ring, or two X substituents are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand,
• provided that at least one R substituent on the or one cyclopentadienyl group is SiR′2NR″2 and
• provided that at least one R substituent on at least one Cp is SiR′2NR″2 and provided that one or the Cp may be bridged by a bridging group to another Cp group, or a heteroatom containing group, where the bridging group replaces one R group on the Cp group(s) or a hydrogen on a heteratom containing group.
• (b) an activator.