Characterization of porphyrin-Co(III)-'nitrene radical' species relevant in catalytic nitrene transfer reactions

Goswami M, Lyaskovskyy V, Domingos SR, Buma WJ, Woutersen S, Tröppner O, Ivanovic-Burmazovic I, Lu H, Cui X, Zhang XP, Reijerse EJ, DeBeer S, van Schooneveld MM, Pfaff FF, Ray K, de Bruin B (2015)

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2015

Journal

Journal of the American Chemical Society American Chemical Society

Publisher: American Chemical Society

Book Volume: 137

Pages Range: 5468-5479

Journal Issue: 16

DOI: 10.1021/jacs.5b01197

Abstract

To fully characterize the Co^III-'nitrene radical' species that are proposed as intermediates in nitrene transfer reactions mediated by cobalt(II) porphyrins, different combinations of cobalt(II) complexes of porphyrins and nitrene transfer reagents were combined, and the generated species were studied using EPR, UV-vis, IR, VCD, UHR-ESI-MS, and XANES/XAFS measurements. Reactions of cobalt(II) porphyrins 1^P1 (P1 = meso-tetraphenylporphyrin (TPP)) and 1^P2 (P2 = 3,5-Di^tBu-ChenPhyrin) with organic azides 2Ns (NsN3), 2Ts (TsN3), and 2Troc (TrocN3) led to the formation of mono-nitrene species 3^P1Ns, 3^P2Ts, and 3^P2Troc, respectively, which are best described as [Co^III(por)(NR″^•-)] nitrene radicals (imidyl radicals) resulting from single electron transfer from the cobalt(II) porphyrin to the 'nitrene' moiety (Ns: R″ = -SO2-p-C6H5NO2; Ts: R″ = -SO2C6H6; Troc: R″ = -C(O)OCH2CCl3). Remarkably, the reaction of 1^P1 with N-nosyl iminoiodane (PhI=NNs) 4Ns led to the formation of a bis-nitrene species 5^P1Ns. This species is best described as a triple-radical complex [(por^•-)Co^III(NR″^•-)2] containing three ligand-centered unpaired electrons: two nitrene radicals (NR″^•-) and one oxidized porphyrin radical (por^•-). Thus, the formation of the second nitrene radical involves another intramolecular one-electron transfer to the "nitrene" moiety, but now from the porphyrin ring instead of the metal center. Interestingly, this bis-nitrene species is observed only on reacting 4Ns with 1^P1. Reaction of the more bulky 1^P2 with 4Ns results again in formation of mainly mono-nitrene species 3^P2Ns according to EPR and ESI-MS spectroscopic studies. The mono- and bis-nitrene species were initially expected to be five- and six-coordinate species, respectively, but XANES data revealed that both mono- and bis-nitrene species are six-coordinate Oh species. The nature of the sixth ligand bound to cobalt(III) in the mono-nitrene case remains elusive, but some plausible candidates are NH3, NH2^-, NsNH^-, and OH^-; NsNH^- being the most plausible. Conversion of mono-nitrene species 3^P1Ns into bis-nitrene species 5^P1Ns upon reaction with 4Ns was demonstrated. Solutions containing 3^P1Ns and 5^P1Ns proved to be still active in catalytic aziridination of styrene, consistent with their proposed key involvement in nitrene transfer reactions mediated by cobalt(II) porphyrins.

Authors with CRIS profile

Oliver Tröppner Lehrstuhl für Bioanorganische Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

How to cite

APA:

Goswami, M., Lyaskovskyy, V., Domingos, S.R., Buma, W.J., Woutersen, S., Tröppner, O.,... de Bruin, B. (2015). Characterization of porphyrin-Co(III)-'nitrene radical' species relevant in catalytic nitrene transfer reactions. Journal of the American Chemical Society, 137(16), 5468-5479. https://dx.doi.org/10.1021/jacs.5b01197

MLA:

Goswami, Monalisa, et al. "Characterization of porphyrin-Co(III)-'nitrene radical' species relevant in catalytic nitrene transfer reactions." Journal of the American Chemical Society 137.16 (2015): 5468-5479.

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