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Coordination Chemistry of Large Diphosphanes − Directional Properties of a Calix[4]arene Proximally Substituted by Two −OCH 2 PPh 2 Podand Arms
Author(s) -
Kuhn Pierre,
Jeunesse Catherine,
Sémeril David,
Matt Dominique,
Lutz Pierre,
Welter Richard
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400411
Subject(s) - chemistry , calixarene , ligand (biochemistry) , methylaluminoxane , coordination complex , chelation , crystallography , denticity , stereochemistry , ethylene , medicinal chemistry , crystal structure , molecule , inorganic chemistry , organic chemistry , catalysis , metal , biochemistry , polymerization , polymer , receptor , metallocene
The proximally‐functionalised calixarene 5,11,17,23‐tetra‐ tert ‐butyl‐25,26‐bis(diphenylphosphanylmethoxy)‐27,28‐dihydroxycalix[4]arene ( 1 ), a large diphosphane in which the P III centres are separated by 10 bonds, behaves as a chelating ligand towards NiX 2 moieties (X = Cl, Br). As shown by three X‐ray studies carried out on complexes of the type [NiX 2 ·1 ], the diphosphane is able to accommodate either tetrahedral or strongly distorted tetrahedral coordination geometries, but not a square planar one. In all structures, the ligand positions the nickel atom away from the calixarene axis. In the presence of methylaluminoxane (MAO), [NiCl 2 ·1 ] effectively catalyses the oligomerisation of ethylene, affording C 4 −C 12 oligomers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)