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Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir and Rh Half‐Sandwich Complexes: A Combined CD/X‐ray Study
Author(s) -
Avello Marta G.,
Frutos María,
de la Torre María C.,
Viso Alma,
Velado Marina,
de la Pradilla Roberto Fernández,
Sierra Miguel A.,
Gornitzka Heinz,
Hemmert Catherine
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702662
Subject(s) - enantiopure drug , chirality (physics) , mesoionic , chemistry , circular dichroism , enantiomer , sulfoxide , cationic polymerization , metal , stereochemistry , vicinal , enantioselective synthesis , crystallography , medicinal chemistry , polymer chemistry , organic chemistry , catalysis , physics , quantum mechanics , quark , chiral symmetry breaking , nambu–jona lasinio model
Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral‐at‐metal Ir III and Rh III half‐sandwich complexes through the synthetic sequence of MIC complexation/C−H aromatic activation. The process was efficient and diastereoselective for the formation of enantiopure five‐membered metallacycles. The use of the enantiomers of the chiral sulfur groups allowed us to prepare complexes that had opposite configurations at the metal center. Complete retention of the configuration at the metal center was observed during the formation of cationic Ir III complexes and upon insertion of alkynes into the Ir III −C bond, as demonstrated by a combined circular dichroism/X‐ray study. These results point to a vicinal‐assisted S N 1‐like mechanism.