Dimeric Rare‐Earth BINOLate Complexes: Activation of 1,4‐Benzoquinone through Lewis Acid Promoted Potential Shifts
- 11 March 2013
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 19 (19), 5996-6004
- https://doi.org/10.1002/chem.201300026
Abstract
Reaction of p‐benzoquinone (BQ) with a series of rare‐earth metal/alkali metal/1,1′‐BINOLate (REMB) complexes (RE: La, Ce, Pr, Nd; M: Li) results in the largest recorded shift in reduction potential observed for BQ upon complexation. In the case of cerium, the formation of a 2:1 Ce/BQ complex shifts the two‐electron reduction of BQ by greater than or equal to 1.6 V to a more favorable potential. Reactivity investigations were extended to other REIII (RE=La, Pr, Nd) complexes where the resulting highly electron‐deficient quinone ligands afforded isolation of the first lanthanide quinhydrone‐type charge‐transfer complexes. The large reduction‐potential shift associated with the formation of 2:1 Ce/BQ complexes illustrate the potential of Ce complexes to function both as a Lewis acid and an electron source in redox chemistry and organic‐substrate activation.Keywords
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