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Title: Tandem Mn-I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate
Author: Uzelac, Marina
Mastropierro, Pasquale
Tullio, Marco
Borilovic, Ivana
Tarres, Marius
Kennedy, Alan R.
Aromí Bedmar, Guillem
Hevia, Eva
Keywords: Liti
Issue Date: 22-Oct-2020
Publisher: Wiley-VCH
Abstract: Pairing lithium and manganese(II) to form lithium manganate [Li2Mn(CH2SiMe3)4] enables the efficient direct Mn-I exchange of aryliodides, affording transient (aryl)lithium manganate intermediates which in turn undergo spontaneous C@C homocoupling at room temperature to furnish symmetrical (bis)aryls in good yields under mild reaction conditions. The combination of EPR with X-ray crystallographic studies has revealed the mixed Li/Mn constitution of the organometallic intermediates involved in these reactions, including the homocoupling step which had previously been thought to occur via a single-metal Mn aryl species. These studies show Li and Mn working together in a synergistic manner to facilitate both the Mn-I exchange and the C@C bond-forming steps. Both steps are carefully synchronized, with the concomitant generation of the alkyliodide ICH2SiMe3 during the Mn-I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant.
Note: Versió postprint del document publicat a:
It is part of: Angewandte Chemie-International Edition, 2020, vol. 60, num. 6, p. 3247-3253
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ISSN: 1433-7851
Appears in Collections:Articles publicats en revistes (Institut de Nanociència i Nanotecnologia (IN2UB))
Articles publicats en revistes (Química Inorgànica i Orgànica)

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