Dimeric Rare‐Earth BINOLate Complexes: Activation of 1,4‐Benzoquinone through Lewis Acid Promoted Potential Shifts |
| |
| Authors: | Jerome R Robinson Corwin H Booth Patrick J Carroll Patrick J Walsh Eric J Schelter |
| |
| Institution: | 1. Department of Chemistry, University of Pennsylvania, 231 S. 34th St. Philadelphia, PA 19104 (USA), Fax: (+215)?573‐2112, Tel: (+215)?898‐8633, Tel: (+215)?573‐2875;2. 1 Cyclotron Rd. MS70?A‐1150, Chemical Sciences Division, Lawrence Berkeley National Laboratory Berkeley, CA 94720 (USA), Fax: (+510)?486‐5596, Tel: (+510)?486‐6079 |
| |
| 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: | electrochemistry lanthanides magnetism oxidation spectroscopy |
|
|
