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Diphosphine Capsules for Transition‐Metal Encapsulation
Author(s) -
Koblenz Tehila S.,
Dekker Henk L.,
de Koster Chris G.,
van Leeuwen Piet W. N. M.,
Reek Joost N. H.
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100092
Subject(s) - cationic polymerization , chemistry , transition metal , metal , ionic bonding , ligand (biochemistry) , stereochemistry , crystallography , polymer chemistry , organic chemistry , ion , catalysis , biochemistry , receptor
Self‐assembly and characterization of novel heterodimeric diphosphine capsules formed by multiple ionic interactions and composed of one tetracationic diphosphine ligand and one complementary tetraanionic calix[4]arene are described. Encapsulation of a palladium atom within a diphosphine capsule is achieved successfully by using the metal complex of the tetracationic diphosphine ligand for the assembly process. In this templated approach to metal encapsulation, the transition‐metal complex is an integrated part of the capsule with the transition metal located inside the capsule and is not involved in the assembly process. We present two approaches for capsule assembly by mixing solutions of the precharged building blocks in methanol and mixing solutions of the neutral building blocks in methanol. The scope of the diphosphine capsules and the metallodiphosphine capsules is easily extended by applying tetracationic diphosphine ligands with different backbones (ethylene, diphenyl ether, and xanthene) and cationic binding motifs ( p ‐C 6 H 4 ‐CH 2 ‐ammonium, m ‐C 6 H 4 ‐ammonium, and m ‐C 6 H 4 ‐guanidinium). These tetracationic building blocks with different flexibilities and shapes readily associate into capsules with the proper capsular structure, as is indicated by 1 H NMR spectroscopy, 1D NOESY, ESI‐MS, and modeling studies.