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Main Title: Ligand spheres in asymmetric hetero Diels-Alder reactions catalyzed by Cu(II) box complexes: experiment and modeling
Author(s): Umamaheswari, V.
Cias, Pawel
Pöppl, Andreas
Kaupp, Martin
Gescheidt, Georg
Type: Article
Language Code: en
Abstract: The stereoselective hetero Diels–Alder reaction between ethyl glyoxylate and cyclohexadiene catalyzed by [Cu(II)t-Bu-(box)](OTf)2 was investigated. The reaction was performed step-by-step and the geometry of the Cu(II) complexes formed in the course of the catalysis was analysed by EPR spectroscopy, advanced pulsed EPR methods (ENDOR, and HYSCORE) and DFT calculations. Our results show that one triflate counterion is directly coordinated to Cu(II) during the catalytic process (axial position). This leads to penta-coordinated Cu(II) complexes. Solvent molecules are able to alter the geometry of the Cu(II) complexes although their coordination is weak. These findings provide an explanation for the solvent and counterion effects observed in many catalytic reactions.
Issue Date: 2014
Date Available: 22-Jun-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Journal Title: Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 43
Issue: 2
Publisher DOI: 10.1039/c3dt51602d
Page Start: 698
Page End: 705
EISSN: 1477-9226
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:Inst. Chemie » Publications

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