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Anion‐Controlled Switching of an X Ligand into a Z Ligand: Coordination Non‐innocence of a Stiboranyl Ligand
Author(s) -
Ke IouSheng,
Jones James S.,
Gabbaï François P.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201309132
Subject(s) - chemistry , ligand (biochemistry) , moiety , medicinal chemistry , chloride , stereochemistry , platinum , fluoride , covalent bond , crystallography , inorganic chemistry , catalysis , organic chemistry , receptor , biochemistry
Abstract The tetravalent platinum stiboranyl complex [(o‐(Ph 2 P)C 6 H 4 ) 2 (o‐C 6 Cl 4 O 2 )Sb]PtCl 2 Ph ( 2 ) has been synthesized by reaction of [(o‐(Ph 2 P)C 6 H 4 ) 2 SbClPh]PtCl ( 1 ) with o ‐chloranil. In the presence of fluoride anions, the stiboranyl moiety of 2 displays non‐innocent behavior and is readily converted into a fluorostiborane unit. This transformation, which is accompanied by elimination of a chloride ligand from the Pt center, results in the formation of [(o‐(Ph 2 P)C 6 H 4 ) 2 (o‐C 6 Cl 4 O 2 )SbF]PtClPh ( 3 ). Structural, spectroscopic, and computational studies show that the conversion of 2 into 3 is accompanied by a cleavage of the covalent PtSb bond present in 2 and formation of a longer and weaker Pt→Sb interaction in 3 . These results show that this new Pt–Sb platform supports the fluoride‐induced metamorphosis of a stiboranyl X ligand into a stiborane Z ligand.