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Seminar on bioinspired inorganic chemistry (Lecture)

Date
Wednesday 20 November 2019Add to my calendar
Time
11:30 to
Location
HG00.303
Description


Program:
11:30 – 12:10         Prof. Lawrence Que, Jr. (University of Minnesota, USA): 'Activating a Sluggish Fe(III)-OOH Intermediate to Hydroxylate Cyclohexane Within Seconds at 233 K'

12:10 – 12:50         Prof. Miquel Costas (University of Girona, Italy): 'Site and enantioselective aliphatic C-H functionalization reactions inspired in nature'

12:50 – 13:05          Guilherme Tripodi (RU, Dept. of Spectroscopy and Catalysis): 'Mass spectrometry approach investigation of short-lived iron(IV)oxo complexes'

13:05 – 13:20          Dr. Erik Andris (RU, Dept. of Spectroscopy and Catalysis): 'Computational design of low-spin iton(IV)oxo complexes'

Abstracts

'Activating a Sluggish Fe(III)-OOH Intermediate to Hydroxylate Cyclohexane Within Seconds at 233 K'
prof. Lawrence QueProf. Lawrence Que, Jr. (University of Minnesora, Minneapolis, United States larryque@umn.edu)

The = ½ FeIII–OOH species [(BnTPEN)FeIII(OOH)]2+ (BnTPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diamino-ethane) has been known for 25 years as a sluggish oxidant. However, the addition of an equivalent of strong acid at 233 K results in its immediate decay and the catalytic hydroxylation of cyclohexane to cyclohexanol. Our studies implicate the generation of a highly reactive FeV=O species via proton-assisted O–O bond heterolysis of the FeIII–OOH intermediate,  analogous to heme enzyme Compound I in its C–H bond cleaving ability.

'Site and enantioselective aliphatic C-H functionalization reactions inspired in nature'
prof. Miquel CostasProf. Miquel Costas (Institut de Quimica Computacional i Catàlisi, Universitat de Girona, Facultat de Ciències, Campus de Montilivi, 17003, Girona, Spain. Miquel.costas@udg.edu)

Aliphatic C-H functionalization reactions are interesting in chemical synthesis because they convert these ubiquitous and poorly reactive bonds into versatile sites for chemical elaboration. The use of metal catalysts that perform this reaction via mechanisms resembling those operating in C-H oxidation enzymes opens the possibility to exert site and stereoselectivity. In this contribution our recent approaches towards designing catalysts for site selective C-H functionalization via carbene1 and oxo2 transfer will be described.

[1] A. Hernán Gómez, M. Rodríguez, T. Parella, M. Costas Angew. Chem. Int. Ed. 2019, 58(39), 13904-13911
[2] M. Milan, M. Salamone, M. Costas, M. Bietti, Acc. Chem, Res. 2018, 51, 1984–1995.

Contact
prof. Jana Roithova