Synthesis, electronic structure and reactivity of bis(imino)pyridine iron carbene complexes: Evidence for a carbene radical

Sarah K. Russell, Jordan M. Hoyt, Suzanne C. Bart, Carsten Milsmann, S. Chantal E. Stieber, Scott P. Semproni, Serena Debeer, Paul J. Chirik

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Abstract

The reactivity of the disubstituted diazoalkane, N2CPh 2 with a family of bis(imino)pyridine iron dinitrogen complexes was examined. For the most sterically protected member of the series, ( iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2C6H3NCMe) 2C5H3N), an S = 1 iron diazoalkane complex was obtained and structurally characterized. Reducing the size of the 2,6-aryl substituents to ethyl or methyl groups resulted in isolation of bis(imino)pyridine iron carbene complexes. Magnetic measurements established S = 1 ground states, demonstrating rare examples of iron carbenes in a weak ligand field. Electronic structure determination using metrical parameters from X-ray diffraction as well as Mössbauer, XAS and computational data established high-spin iron(ii) compounds engaged in antiferromagnetic coupling with redox-active bis(imino)pyridine and carbene radicals.

Original languageEnglish (US)
Pages (from-to)1168-1174
Number of pages7
JournalChemical Science
Volume5
Issue number3
DOIs
StatePublished - Mar 2014

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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    Russell, S. K., Hoyt, J. M., Bart, S. C., Milsmann, C., Stieber, S. C. E., Semproni, S. P., Debeer, S., & Chirik, P. J. (2014). Synthesis, electronic structure and reactivity of bis(imino)pyridine iron carbene complexes: Evidence for a carbene radical. Chemical Science, 5(3), 1168-1174. https://doi.org/10.1039/c3sc52450g