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Unusually Large Bite Angle of a Distally Diphosphanylated Calix[4]arene Chelator
Author(s) -
Sameni Soheila,
Jeunesse Catherine,
Awada Mouhamad,
Matt Dominique,
Welter Richard
Publication year - 2010
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.201000595
Subject(s) - bite angle , chemistry , bent molecular geometry , crystallography , ligand (biochemistry) , calixarene , chelation , crystal structure , atom (system on chip) , nickel , aromaticity , stereochemistry , molecule , inorganic chemistry , organic chemistry , receptor , biochemistry , denticity , computer science , embedded system
5,17‐Diphenylphosphanyl‐11,23‐bis(4‐tolyl)‐25,26,27,28‐tetrapropoxycalix[4]arene ( 6 ), a semi‐rigid, calixarene‐based diphosphane in which the phosphorus atoms are separated by 12 chemical bonds, reacts with [Ni(η 5 ‐C 5 H 5 )(1,5‐cyclooctadiene)]BF 4 or AgBF 4 to afford the corresponding chelate complexes [Ni(η 5 ‐C 5 H 5 )( 6 )]BF 4 and [Ag( 6 )]BF 4 quantitatively. These complexes were both characterised by a single‐crystal X‐ray diffraction study. In the nickel complex the ligand shows a bite angle of 104.5°, which lies in the range expected for this kind of diphosphane with a large P ··· P separation. In the silver(I) complex the diphosphane displays a much larger bite angle of 138.8°, which was unexpected and reflects the flexilibilty of the calix[4]arene skeleton. Furthermore, in solution the silver complex shows dynamic behaviour. One of the observed motions corresponds to the silver atom switching reversibly from a linear to a bent AgP 2 cordination geometry.