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The iron(III) complex [Fe(tpena)] 2+ (tpena = N,N,N′-tris(2-pyridylmethyl)ethylendiamine-N′-acetate) undergoes irreversible O 2 -dependent N-demethylcarboxylation to afford [Fe II (SBPy3)(MeCN)] 2+ (SBPy3 = N,N-bis(2pyridylmethyl)amine-N-ethyl-2-pyridine-2-aldimine), when irradiated with near-UV light. The loss of a mass equivalent to the glycyl group in a process involving consecutive C−C and C−N cleavages is documented by the measurement of the sequential production of CO 2 and formaldehyde, respectively. Time-resolved UV−vis absorption, Mossbauer, EPR, and Raman spectroscopy have allowed the spectroscopic characterization of two iron-based intermediates along the pathway. The first of these, proposed to be a low-spin iron(II)-radical ligand complex, reacts with O 2 in the rate-determining step to produce a putative alkylperoxide complex. DFT calculations suggest that this evolves into an Fe(IV)-oxo species, which can abstract a hydrogen atom from a cis methylene group of the ligand to give the second spectroscopically identified intermediate, a high-spin iron(III)-hydroxide of the product oxidized ligand, [Fe III (OH)(SBPy 3 )] 2+ . Reduction and exchange of the cohydroxo/water ligand produces the crystallographically characterized products [Fe II (SBPy3)(X)] 2+/3+ , X = MeCN, [Zn(tpena)] + .

Dedicated Professor Pablo Espinet on the occasion of his 70th birthdayAbstract: The computational characterization of the full catalytic cycle for the synthesis of indoline from the reaction between iodoacetanilide and at erminal alkene catalyzed by an ickel complex and ap hotoactive ruthenium species is presented. Avariety of oxidation states of nickel, Ni 0 ,Ni I ,Ni II , and Ni III ,i ss hown to participate in the mechanism. Ni 0 is necessary for the oxidative addition of the CÀIb ond, which goes through aN i I intermediate and results in aN i II species. The Ni II species inserts into the alkene,b ut does not undergo the reductive elimination necessary for CÀNb ond formation. This oxidatively induced reductive elimination can be accomplished only after oxidation to Ni III by the photoactive ruthenium species.A ll the reaction steps are computationally characterized,a nd the barriers for the single-electron transfer steps calculated using am odified version of the Marcus Theory.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines. Under dirhodium catalysis, α-imino carbenes were generated and formed nitrogen ylide intermediates that, after subsequent aminal opening, afforded...

The mechanisms of aqueous methanol dehydrogenation reaction catalyzed by defined Mn and Re pincer complexes under different conditions were computed.