Low-Temperature N_2 Binding to Two-Coordinate L_2Fe^0 Enables Reductive Trapping of L_2FeN_2^- and NH_3 Generation
- Creators
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Ung, Gaël
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Peters, Jonas C.
Abstract
The two-coordinate [(CAAC)_2Fe] complex [CAAC=cyclic (alkyl)(amino)carbene] binds dinitrogen at low temperature (T<−80 °C). The resulting putative three-coordinate N_2 complex, [(CAAC)_2Fe(N_2)], was trapped by one-electron reduction to its corresponding anion [(CAAC)_2FeN_2]^− at low temperature. This complex was structurally characterized and features an activated dinitrogen unit which can be silylated at the β-nitrogen atom. The redox-linked complexes [(CAAC)_2Fe^I][BAr^F_4], [(CAAC)_2Fe^0], and [(CAAC)_2Fe^(−I)N_2]^− were all found to be active for the reduction of dinitrogen to ammonia upon treatment with KC_8 and HBAr^F_4^(⋅2) Et_2O at −95 °C [up to (3.4±1.0) equivalents of ammonia per Fe center]. The N_2 reduction activity is highly temperature dependent, with significant N_2 reduction to NH_3 only occurring below −78 °C. This reactivity profile tracks with the low temperatures needed for N_2 binding and an otherwise unavailable electron-transfer step to generate reactive [(CAAC)_2FeN_2]^−.
Additional Information
© 2014 Wiley-VCH Verlag GmbH & Co. Manuscript Received: 24 Sep 2014. Article first published online: 13 Non 2014. Early View (Online Version of Record published before inclusion in an issue). This work was supported by the NIH (GM 070757) and the Gordon and Betty Moore Foundation. We thank Larry Henling and Michael K. Takase for crystallographic assistance.Attached Files
Accepted Version - nihms642891.pdf
Supplemental Material - anie_201409454_sm_miscellaneous_information.pdf
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Additional details
- PMCID
- PMC4314396
- Eprint ID
- 52098
- Resolver ID
- CaltechAUTHORS:20141124-110523536
- NIH
- GM 070757
- Gordon and Betty Moore Foundation
- Created
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2014-11-24Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field