What question did this study set out to answer?

To synthesize sterically hindered dipyrromethene iron complexes and investigate their catalytic ability and mechanistic pathway in C–H bond amination and olefin aziridination.

March 15, 2011Journal of the American Chemical SocietyOpen Access

Catalytic C−H Bond Amination from High-Spin Iron Imido Complexes

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To synthesize sterically hindered dipyrromethene iron complexes and investigate their catalytic ability and mechanistic pathway in C–H bond amination and olefin aziridination.
Synthesized sterically encumbered dipyrromethene ligands with alkyl and aryl flanking groups to isolate high-spin (S=2), three- and four-coordinate iron(II) precatalysts.
Conducted catalytic C–H amination of toluene and aziridination of styrene using organic azides at room temperature, measuring primary kinetic isotope effects.
Isolated a terminal high-spin iron imido intermediate and characterized its geometric and electronic structure via 1H NMR, X-ray crystallography, 57Fe Mössbauer spectroscopy, and DFT calculations.
Catalysis with ((Ad)L)FeCl(OEt2) achieved 12 turnovers for toluene amination and >85% conversion to aziridine with styrene, yielding a primary kinetic isotope effect of 12.8(5).
The isolated terminal imido complex ((Ar)L)FeCl(N(p-(t)BuC6H4)) exhibited an elongated Fe–N bond of 1.768(2) Å and an electronic structure consisting of a high-spin Fe(III) center antiferromagnetically coupled to an imido radical (J = -673 cm⁻¹).
Stoichiometric nitrene transfer from the isolated imido complex afforded 42% amination yield in toluene with a kinetic isotope effect of 24(3) and 76% aziridine yield in styrene, confirming its role as a catalytic intermediate.

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Implication

Mechanistic study demonstrates room-temperature C–H amination using high-spin iron complexes, indicating that reactive iron-imido radicals drive catalytic nitrene transfer.

Cite This Study

King et al. (2011) studied this question.

synapsesocial.com/papers/6a001f68b124fe581985c4d3 https://doi.org/10.1021/ja110066j

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Implication

Mechanistic study demonstrates room-temperature C–H amination using high-spin iron complexes, indicating that reactive iron-imido radicals drive catalytic nitrene transfer.

Catalytic C−H Bond Amination from High-Spin Iron Imido Complexes

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Discussion

Implication

Cite This Study

Catalytic C−H Bond Amination from High-Spin Iron Imido Complexes

Key Points

Discussion

Implication

Cite This Study

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