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The “Dendritic Effect” in Homogeneous Catalysis with Carbosilane‐Supported Arylnickel( II ) Catalysts: Observation of Active‐Site Proximity Effects in Atom‐Transfer Radical Addition
Author(s) -
Kleij Arjan W.,
Gossage Robert A.,
Jastrzebski Johann T. B. H.,
Boersma Jaap,
van Koten Gerard
Publication year - 2000
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(20000103)39:1<176::aid-anie176>3.0.co;2-3
Subject(s) - dendrimer , catalysis , homogeneous , chemistry , atom (system on chip) , nickel , homogeneous catalysis , redox , molecule , heterogeneous catalysis , photochemistry , polymer chemistry , organic chemistry , thermodynamics , physics , computer science , embedded system
Advantages of homo‐ and heterogeneous catalysts are united in metallodendritic molecules where nickel‐based catalysts are bound to carbosilane dendrimers. The first direct indication of a “dendritic effect” in the redox catalysis behavior is described: variation of the dendrimer support controls the proximity of the Ni II centers, which in turn controls catalytic activity. Catalyst deactivation, by means of Ni III formation, can be avoided by a larger separation of the Ni II centers (see picture).