Author: Julio Lloret-fillol

Evidence that steric factors modulate reactivity of tautomeric iron-oxo species in stereospecific alkane C-H hydroxylation

A new iron complex mediates stereospecific hydroxylation of alkyl C-H bonds with hydrogen peroxide, exhibiting excellent efficiency. Isotope labelling studies provide evidence that the relative reactivity of tautomerically related oxo-iron species responsible for the C-H hydroxylation reaction is dominated by steric factors This work has been supported by the European Union (the Erasmus Mundus program), the International Research Training Group Metal Sites in Biomolecules: Structures, Regulation and Mechanisms (www.biometals.eu), and COST Action CM1003. M.C. acknowledges ERC-29910, MINECO of Spain for CTQ2012- 37420-C02-01/BQU and CSD2010-00065, catalan DIUE (2009SGR637) and an ICREA academ…

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The synergy between the CsPbBr3 nanoparticle surface and the organic ligand becomes manifest in a demanding carbon–carbon coupling reaction

We demonstrate here the suitability of CsPbBr3nanoparticles as photosensitizers for a demanding photoredox catalytic homo- and cross-coupling of alkyl bromides at room temperature by merely using visible light and an electron donor, thanks to the cooperative action between the nanoparticle surface and organic capping. Fil: Rosa-Pardo, Ignacio. Instituto de Ciencia Molecular; España. Universidad de Valencia; España Fil: Casadevall, Carla. Barcelona Institute Of Science And Technology. Institut Català D'investigació Química.; España Fil: Schmidt, Luciana Carina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigac…

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Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV–Oxo Intermediate

The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at −40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mossbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl pero…

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Understanding light-driven H2 evolution through the electronic tuning of aminopyridine cobalt complexes† †Electronic supplementary information (ESI) available. CCDC 1578284–1578289. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04328g

Electronic effects provide a general mechanistic scenario for rationalizing photocatalytic water reduction activity with aminopyridine cobalt complexes.

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Understanding light-driven H 2 evolution through the electronic tuning of aminopyridine cobalt complexes

A new family of cobalt complexes with the general formula [CoII(OTf)2(Y,XPyMetacn)] (1R,Y,XPyMetacn ¼ 1-[(4-X-3,5-Y-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, (X ¼ CN (1CN), CO2Et (1CO2Et), Cl (1Cl), H(1H), NMe2 (1NMe2)) where (Y ¼ H, and X ¼ OMe when Y ¼ Me (1DMM)) is reported. We found that the electronic tuning of the Y,XPyMetacn ligand not only has an impact on the electronic and structural properties of the metal center, but also allows for a systematic water-reduction-catalytic control. In particular, the increase of the electron-withdrawing character of the pyridine moiety promotes a 20-fold enhancement of the catalytic outcome. By UV-Vis spectroscopy, luminescence quenc…

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Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis

The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru II(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times.…

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CCDC 1418388: Experimental Crystal Structure Determination

Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564

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CCDC 960139: Experimental Crystal Structure Determination

Related Article: Mainak Mitra, Julio Lloret-Fillol, Matti Haukka, Miquel Costas, Ebbe Nordlander|2014|Chem.Commun.|50|1408|doi:10.1039/C3CC47830K

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CCDC 1033835: Experimental Crystal Structure Determination

Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564

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