Selective preparation of racemic metallocene complexes, used as catalysts

摘要

Racemic metallocene complexes (I) are prepared from bridged transition metal phenolate complexes (II) and alkali metal or alkaline earth metal cyclopentadienyl derivatives. Some (I) are new. Preparation of racemic metallocene complexes (I) involves reaction of bridged transition metal phenolate complexes of formula (II) with alkali metal or alkaline earth metal (preferably magnesium) cyclopentadienyl derivatives and optionally subsequently substituting the bridged phenolate ligands. M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Group III transition metal or lanthanoid; X = halo, H, alkyl, Ar, alkylaryl, OR10 or NR10R11; n = 1-4, i.e. the valency of M minus 2; R1,R8 = halo, 1-20C alkyl, 3-8C cycloalkyl (optionally substituted by alkyl), alkylaryl, arylalkyl or Si(R9)3; R9 = 1-20C alkyl, cycloalkyl or Ar; R2-R8 = H; or as R1 with the exception of halo; R2-R7 = adjacent groups optionally forming 4-15 C saturated, partially saturated or unsaturated cyclic group; residues in R1-R9 = optionally, partially or completely substituted by heteroatoms; R10,R11 = alkyl, Ar, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl; Y,Y1 = Q, Q-Q, Q-Q', Q', O-Q, Q'-Q', BR12, AlR12, Ge, Sn, O, S, SO, SO2, NR12, CO, PR12 or P(O)R12; Q = M1(R12)2; Q' = C(R12)2; R12 = H, halo, alkyl, fluoroalkyl, 6-10 C fluoroaryl, 6-10 C aryl, alkoxy, 2-10 C alkenyl, 7-40 C arylalkyl, 8-40 C arylalkenyl or 7-40 C alkylaryl; or two R12 groups together complete a ring; M1 = Si, Ge or Sn; m = 0-3; Ar = 6-15 C aryl. Unless specified otherwise alkyl moieties have 1-10 C, aryl 6-20 C and cycloalkyl 3-10 C. An Independent claim relates to novel racemic metallocene complex products of formula (I'): X1 = group of formula (i); Z = group of formula (ii); E = A or group of formula (iii); R13-R17, R19-R23 = H, 1-20 C alkyl, 5-7 membered cycloalkyl (optionally substituted by alkyl), Ar or arylalkyl (C-number not specified) (where adjacent groups can form a 4-15 C cyclic group); or Si(R)3; or R16 + Z = -(T(R25)(R26))q-E-; R25,R26 = H, 1-20 C alkyl, cycloalkyl or Ar; q = 1-4; A = O, S, NR27 or PR27; R27 = alkyl, Ar, cycloalkyl, alkylaryl (C-number not specified) or Si(R28)3; R28 = alkyl, Ar, cycloalkyl or alkylaryl (C-number not specified).