4.8 Article

Diferrocenophosphaborin: A Planar-Chiral, Redox-Active and Anion-Responsive Ambiphilic Ligand

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 35, Pages 10202-10205

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201504922

Keywords

ambiphilic ligands; ferrocenes; Lewis acids; planar chirality; redox activity

Funding

  1. Petroleum Research Fund [45648-AC3]
  2. National Science Foundation [CRIF 0443538, MRI 1229030]
  3. Rutgers University
  4. Petroleum Research Fund (ACS SUMR)
  5. Direct For Mathematical & Physical Scien [1229030] Funding Source: National Science Foundation
  6. Division Of Chemistry [1229030] Funding Source: National Science Foundation

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A new class of Janus-like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4-SnP and 4-BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single-crystal X-ray studies. In addition, the ligands are redox-responsive and the Lewis acidic borane moiety in 4-BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska-type RhI complex 5-BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding.

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