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
In: Chemistry (Weinheim an der Bergstrasse, Germany), Jg. 23 (2017-06-09), Heft 58
Online
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Zugriff:
Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral-at-metal Ir and Rh 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 complexes and upon insertion of alkynes into the Ir−C bond, as demonstrated by a combined circular dichroism/X-ray study. These results point to a vicinal-assisted S1-like mechanism.
Support for this work under grants CTQ2013-46459-C2-01-P, CTQ2016-77555-C2-1-R to M.A.S., CTQ2013-46459-C2-02-P, CTQ2016-77555-C2-2-R to M.C.T. and CTQ2014-51912-REDC Programa Redes Consolider, from the MINECO (Spain) is gratefully acknowledged. M.G.A. and M.F.P. thanks the MINECO for FPI grants.
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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
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Autor/in / Beteiligte Person: | María C. de la Torre ; Velado, Marina ; Roberto Fernández de la Pradilla ; Viso, Alma ; Sierra, Miguel A. ; Hemmert, Catherine ; Avello, Marta G. ; Frutos, María ; Gornitzka, Heinz ; Ministerio de Economía, Industria y Competitividad (España) ; CSIC-IQOG ; Centro de Innovación en Química Avanzada (ORFEO−CINQA Network) (ORFEO−CINQA) ; Departamento de Química Orgánica I, Facultad de Química, Universidad Complutense ; Universidad Complutense de Madrid = Complutense University of Madrid [Madrid] (UCM) ; Laboratoire de chimie de coordination (LCC) ; Institut National Polytechnique (Toulouse) (Toulouse INP) ; Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3) ; Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599) ; Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) ; Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) ; Université Toulouse III - Paul Sabatier (UT3) ; Université Fédérale Toulouse Midi-Pyrénées |
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Zeitschrift: | Chemistry (Weinheim an der Bergstrasse, Germany), Jg. 23 (2017-06-09), Heft 58 |
Veröffentlichung: | 2017 |
Medientyp: | unknown |
ISSN: | 1521-3765 (print) ; 0947-6539 (print) |
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