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Enhancing Electrophilic Alkene Activation by Increasing the Positive Net Charge in Transition‐Metal Complexes and Application in Homogeneous Catalysis
Author(s) -
Hahn Christine
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400550
Subject(s) - alkene , electrophile , catalysis , nucleophile , chemistry , transition metal , cationic polymerization , homogeneous , metal , homogeneous catalysis , photochemistry , computational chemistry , organic chemistry , thermodynamics , physics
Among a large variety of fine‐tuning parameters for homogeneous catalysts the net charge of transition‐metal complexes appear to be an interesting factor that considerably affects activation of substrates and catalytic activity in general. The electrophilicity of coordinated alkenes in transition‐metal complexes can be strongly enhanced by increasing the positive net charge, resulting in strong carbocationic properties. Theoretical and experimental studies have shown that the alkene in cationic complexes is kinetically and thermodynamically more activated towards nucleophilic addition than in neutral complexes. The concept of increasing the positive complex charge is thought to be useful for the development of new catalysts for reactions in which alkenes or other unsaturated substrates are involved.