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

Abstract

Pairing lithium and manganese(II) to form lithium manganate [Li₂ Mn(CH₂ SiMe₃ )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 ICH₂ SiMe₃ during the Mn-I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant.

Keywords: cooperative effects; homocoupling; lithium; manganese; structure elucidation.