Journal article
Dramatically accelerated selective oxygen-atom transfer by a nonheme iron(IV)-oxo complex: Tuning of the first and second coordination spheres
LR Widger, CG Davies, T Yang, MA Siegler, O Troeppner, GNL Jameson, I Ivanović-Burmazović, DP Goldberg
Journal of the American Chemical Society | AMER CHEMICAL SOC | Published : 2014
DOI: 10.1021/ja410240c
Open access
Abstract
The new ligand N3PyamideSR and its FeII complex [FeII(N3PyamideSR)](BF4)2 (1) are described. Reaction of 1 with PhIO at -40 C gives metastable [Fe IV(O)(N3PyamideSR)]2+ (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe II(Cl)(N3PyamideSR)](BF4)2 (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe II(N3PyamideS(O)R)](BF4)2 (4). Catalytic OAT with 1 was also observed. © 2014 American Chemical Society.
Grants
Awarded by National Institute of General Medical Sciences
Funding Acknowledgements
The NIH (D.P.G., GM62309 and GM101153) is gratefully acknowledged for financial support. G.N.L.J. thanks the Marsden Fund and The International Mobility Fund administered by Royal Society of New Zealand. I. I.-B. and O. T. gratefully acknowledge support through the "Solar Technologies Go Hybrid" initiative of the German Federate State of Bavaria.