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Tandem Mn-I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate

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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.

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UZELAC, Marina, et al. Tandem Mn-I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate. Angewandte Chemie-International Edition. 2020. Vol. 60, num. 6, pags. 3247-3253. ISSN 1433-7851. [consulted: 13 of August of 2026]. Available at: https://hdl.handle.net/2445/185254

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