Journal article
Generation of a high-valent iron imido corrolazine complex and NR group transfer reactivity
P Leeladee, GNL Jameson, MA Siegler, D Kumar, SP De Visser, DP Goldberg
Inorganic Chemistry | AMER CHEMICAL SOC | Published : 2013
DOI: 10.1021/ic400280x
Abstract
The generation of a new high-valent iron terminal imido complex prepared with a corrolazine macrocycle is reported. The reaction of [Fe III(TBP8Cz)] (TBP8Cz = octakis(4-tert- butylphenyl)corrolazinato) with the commercially available chloramine-T (Na +TsNCl-) leads to oxidative N-tosyl transfer to afford [FeIV(TBP8Cz+•)(NTs)] in dichloromethane/acetonitrile at room temperature. This complex was characterized by UV-vis, Mössbauer (δ = -0.05 mm s-1, ΔE Q = 2.94 mm s-1), and EPR (X-band (15 K), g = 2.10, 2.00) spectroscopies, and together with reactivity patterns and DFT calculations has been established as an iron(IV) species antiferromagnetically coupled with a Cz-π-cation-radical (Stotal = 1..
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Awarded by Engineering and Physical Sciences Research Council
Funding Acknowledgements
This work was supported by the NSF (CHE0909587 and CHE1213836 to D.P.G.). P.L. is grateful for the Queen Sirikit Scholarship (Thailand). We thank Dr. Yosra M. Badiei for the synthesis of <SUP>57</SUP>FeCl<INF>2</INF> and Dr. Victoria J. A. Jameson for help with Mossbauer sample preparation. The computational work was supported by CPU time provided by the National Service of Computational Chemistry Software (NSCCS). D.K. holds a Ramanujan Fellowship from the Department of Science and Technology (DST), New Delhi (India), and acknowledges its financial support (Research Grants SR/S2/RJN-11/2008 and SR/S1/PC-58/2009).