Synthesis and redox reactivity of a phosphine-ligated dichromium paddlewheel

Reed J. Eisenhart, Rebecca K. Carlson, Kelsey M. Boyle, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


A pentadentate ligand platform, bis[2-(diisopropylphosphino-methylamino)phenyl]ether (1), abbreviated as H2(PNONP), is introduced that enables the isolation of homodinuclear chromium complexes. In a one-step metalation using Cr(III) and Cr(II) chloride reagents, the bimetallic compounds, [Cr(μ-Cl)(PNONP)]2 (2) and [Cr(PNONP)]2 (3), respectively, were synthesized. These complexes have been characterized by X-ray diffraction, NMR spectroscopy, cyclic voltammetry, magnetometry, UV-Vis-NIR spectroscopy, combustion analysis, and computational methods. Complex 3 has a reasonably short Cr-Cr bond length of 2.1342(5) Å. Quantum chemical calculations support a diradical singlet ground-state with a formal triple bond between the chromium centers. By cyclic voltammetry, 3 exhibits two reversible oxidations at E = -470 and -750 mV versus FeCp20/+. The one- and two-electron oxidized analogues, 3+ and 32+, were generated in situ via chemical oxidation using ferrocenium. Based on in situ characterization of 3+ and 32+, we hypothesize the oxidations are metal-based to yield Cr25+ and Cr26+ cores, respectively.

Original languageEnglish (US)
Pages (from-to)336-344
Number of pages9
JournalInorganica Chimica Acta
StatePublished - Jan 1 2015

Bibliographical note

Publisher Copyright:
© 2014 Elsevier B.V. All rights reserved.


  • Dichromium
  • Dinuclear
  • Homobimetallic
  • Metal-metal multiple bond
  • Phosphine


Dive into the research topics of 'Synthesis and redox reactivity of a phosphine-ligated dichromium paddlewheel'. Together they form a unique fingerprint.

Cite this