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Kinetics of substitution at ternary titanium(IV)–cyclopentadienyl, pyronato or pyridinato–halide or alkoxide complexes
Author(s) -
Burgess John,
Parsons Simon A
Publication year - 1993
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.590070508
Subject(s) - chemistry , alkoxide , acetonitrile , cyclopentadienyl complex , halide , titanium , medicinal chemistry , cyclopentadiene , ligand (biochemistry) , substitution reaction , ternary operation , inorganic chemistry , thiocyanate , reaction rate constant , kinetics , organic chemistry , catalysis , computer science , biochemistry , receptor , programming language , physics , quantum mechanics
Rate laws and kinetic parameters are reported for substitution at titanium(IV) complexes Ti(LL) 2 X 2 , where LLH=cyclopentadiene, the 4‐pyrone ethylmaltol, several 4‐pyridinones, and related ligands, and X=halide or alkoxide, in acetonitrile solution at 298.2 K. Reactivities are discussed in terms of the nature of the leaving group, the entering group and the non‐leaving ligand LL − . Activation volumes of −15 and −12 cm 3 mol −1 have been determined for thiocyanate attack at Ti(cp) 2 Cl 2 and Ti(etmalt) 2 Cl 2 respectively. Substitution mechanisms are discussed in the light of the kinetic parameters obtained.