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Dimeric Rare‐Earth BINOLate Complexes: Activation of 1,4‐Benzoquinone through Lewis Acid Promoted Potential Shifts
Author(s) -
Robinson Jerome R.,
Booth Corwin H.,
Carroll Patrick J.,
Walsh Patrick J.,
Schelter Eric J.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300026
Subject(s) - chemistry , cerium , redox , lewis acids and bases , lanthanide , quinone , benzoquinone , reactivity (psychology) , one electron reduction , electron transfer , electron affinity (data page) , metal , inorganic chemistry , photochemistry , stereochemistry , ion , molecule , organic chemistry , catalysis , electrochemistry , medicine , alternative medicine , pathology , electrode
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 RE III (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.
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