Synthesis, electronic structure and reactivity of bis(imino)pyridine iron carbene complexes: evidence for a carbene radicalElectronic supplementary information (ESI) available: Complete experimental procedures, characterization data for all new compounds and computational results. CCDC 957144-957116. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c3sc52450g

• Main Authors: Russell, Sarah K, Hoyt, Jordan M, Bart, Suzanne C, Milsmann, Carsten, Stieber, S. Chantal E, Semproni, Scott P, DeBeer, Serena, Chirik, Paul J
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c3sc52450g

The reactivity of the disubstituted diazoalkane, N 2 CPh 2 with a family of bis(imino)pyridine iron dinitrogen complexes was examined. For the most sterically protected member of the series, ( iPr PDI)Fe(N 2 ) 2 ( iPr PDI = 2,6-(2,6- i Pr 2 C 6 H 3 N&z.dbd;CMe) 2 C 5 H 3 N), 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. The reactivity of the disubstituted diazoalkane, N 2 CPh 2 with a family of bis(imino)pyridine iron dinitrogen complexes was examined.