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Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species.

ABSTRACT: High-valent terminal copper-nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper-nitrene intermediate was trapped at -90?°C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)-nitrene radical species that is stable at room temperature in the absence of any Lewis acid. The azide derivative of a triazamacrocyclic ligand that had previously been utilized in the stabilization of aryl-CuIII intermediates was employed as an ancillary ligand in the study. The terminal copper(II)-nitrene radical species is able to transfer a nitrene moiety to phosphines and abstract a hydrogen atom from weak C-H bonds, leading to the formation of oxidized products in modest yields.

SUBMITTER: Corona T

PROVIDER: S-EPMC5154675 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species.

Corona Teresa T Ribas Lídia L Rovira Mireia M Farquhar Erik R ER Ribas Xavi X Ray Kallol K Company Anna A

Angewandte Chemie (International ed. in English) 20161010 45

High-valent terminal copper-nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper-nitrene intermediate was trapped at -90 °C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic cha ...[more]

PMID: 27723252

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Project description: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(t)Bu-ChenPhyrin) with organic azides 2(Ns) (NsN3), 2(Ts) (TsN3), and 2(Troc) (TrocN3) led to the formation of mono-nitrene species 3(P1)(Ns), 3(P2)(Ts), and 3(P2)(Troc), 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) 4(Ns) led to the formation of a bis-nitrene species 5(P1)(Ns). 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 4(Ns) with 1(P1). Reaction of the more bulky 1(P2) with 4(Ns) results again in formation of mainly mono-nitrene species 3(P2)(Ns) 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 O(h) 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(P1)(Ns) into bis-nitrene species 5(P1)(Ns) upon reaction with 4(Ns) was demonstrated. Solutions containing 3(P1)(Ns) and 5(P1)(Ns) 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.

Dataset Information

Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species.

Publications

Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species.

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