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Tandem Mn–I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate
Author(s) -
Uzelac Marina,
Mastropierro Pasquale,
Tullio Marco,
Borilovic Ivana,
Tarrés Màrius,
Kennedy Alan R.,
Aromí Guillem,
Hevia Eva
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013153
Subject(s) - manganate , chemistry , lithium (medication) , manganese , aryl , electron paramagnetic resonance , transmetalation , inorganic chemistry , comproportionation , combinatorial chemistry , medicinal chemistry , organic chemistry , electrochemistry , catalysis , battery (electricity) , electrode , nuclear magnetic resonance , medicine , power (physics) , physics , quantum mechanics , alkyl , endocrinology
Pairing lithium and manganese(II) to form lithium manganate [Li 2 Mn(CH 2 SiMe 3 ) 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 ICH 2 SiMe 3 during the Mn–I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant.