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Understanding and utilizing the dynamic quantum properties of metal ions is the frontier of many next generation technologies. One property in particular, magnetic relaxation, is a complicated physical phenomenon that is scarcely treated in undergraduate coursework. Consequently, principles of magnetic relaxation are nearly impenetrable to starting synthetic chemists, who ultimately design the molecules that fuel new discoveries. In this Tutorial Review, we describe a new paradigm for thinking of magnetic relaxation in metal complexes in terms of a simple reaction-coordinate diagram to facilitate access to the field. We cover the main mechanisms of both spin-lattice (T1) and spin-spin (T2) relaxation times within this conceptual framework and how molecular and environmental design affects these times. Ultimately, we show that many of the scientific methods used by inorganic chemists to study and manipulate reactivity are also useful for understanding and controlling magnetic relaxation. We also describe the cutting edge of magnetic relaxation within this paradigm.
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Borolides (BC42-) can be considered as dianionic heterocyclic analogues of monoanionic cyclopentadienides. Although both are formally six-π-electron donors, we herein demonstrate that the electronic structure of their corresponding transition metal complexes differs significantly, leading to altered properties. Specifically, the 18-electron sandwich complex Ni(iPr2NBC4Ph2)2 (1) features an â¼90° angle between the Ni-B-N planes and is best described as a combination of three limiting resonance structures with the major contribution stemming from a formally Ni2+ species bound to two monoanionic radical (BC4â¢-) ligands. Compound 1 displays two sequential one-electron oxidation events over a small potential range of <0.2 V, which strikingly contrasts the large potential separations between redox partners in the family of metallocenes, and the potential reasons for this unusual observation are discussed.
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tert-Butoxide unlocks new reactivity patterns embedded in nitroarenes. Exposure of nitrostilbenes to sodium tert-butoxide was found to produce N-hydroxyindoles at room temperature without an additive. Changing the counterion to potassium changed the reaction outcome to yield solely oxindoles through an unprecedented dioxygen-transfer reaction followed by a 1,2-phenyl migration. Mechanistic experiments established that these reactions proceed via radical intermediates and suggest that counterion coordination controls whether an oxindole or N-hydroxyindole product is formed.
Assuntos
Butanóis/química , Indóis/química , Nitrocompostos/química , Oxindóis/química , Estilbenos/química , Transporte de Elétrons , Estrutura MolecularRESUMO
The electrocatalytic reduction of carbon dioxide (CO2) could be a powerful tool for generating chemical fuels and feedstock molecules relevant to the chemical industry. One of the major challenges for molecular catalysts remains the necessity of high overpotentials, which can be overcome by identifying novel routes that improve the energetic reaction trajectory of critical intermediates during catalysis. In this combined experimental and computational study, we show that imidazolium functionalization of molecular fac-Mn(CO)3 bipyridine complexes results in CO2 reduction at mild electrochemical potentials in the presence of H2O. Importantly, our studies suggest that imidazolium groups in the secondary coordination sphere promote the formation of a local hydration shell that facilitates the protonation of CO2 reduction intermediates. As such, we propose a synergistic relationship between the functionalized catalyst and H2O, which stands in contrast to other systems in which the presence of H2O frequently has detrimental effects on catalysis.
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We present the first examples of CO2 electro-reduction catalysts that feature charged imidazolium groups in the secondary coordination sphere. The functionalized Lehn-type catalysts display significant differences in their redox properties and improved catalytic activities as compared to the conventional reference catalyst. Our results suggest that the incorporated imidazolium moieties do not solely function as a charged tag but also alter mechanistic aspects of catalysis.
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Background: Dapagliflozin formate (DAP-FOR, DA-2811), an ester prodrug of dapagliflozin, was developed to improve the stability and pharmaceutical manufacturing process of dapagliflozin, a sodium-glucose cotransporter-2 inhibitor. Purpose: This study aimed to evaluate the pharmacokinetics (PKs) and safety of dapagliflozin for DAP-FOR compared to those for dapagliflozin propanediol monohydrate (DAP-PDH, Forxiga) in healthy subjects. Methods: This was an open-label, randomized, single-dose, two-period, two-sequence crossover study. The subjects received a single dose of DAP-FOR or DAP-PDH 10 mg in each period, with a 7-day washout. Serial blood samples for PK analysis were collected up to 48 hours after a single administration to determine plasma concentrations of DAP-FOR and dapagliflozin. PK parameters were calculated using a non-compartmental method and compared between the two drugs. Results: In total, 28 subjects completed the study. DAP-FOR plasma concentrations were not detected in all of the blood sampling time points except for one time point in one subject, and the corresponding DAP-FOR plasma concentration in the subject was close to the lower limit of quantification. The mean plasma concentration-time profiles of dapagliflozin were comparable between the two drugs. The geometric mean ratios and its 90% confidence intervals of the maximum plasma concentration and area under the plasma concentration-time curve of dapagliflozin for DAP-FOR to DAP-PDH were within the conventional bioequivalence range of 0.80-1.25. Both drugs were well-tolerated, with a similar incidence of adverse drug reactions. Conclusion: The rapid conversion of DAP-FOR into dapagliflozin led to the extremely low exposure of DAP-FOR and comparable PK profiles of dapagliflozin between DAP-FOR and DAP-PDH. The safety profiles were also similar between the two drugs. These results suggest that DAP-FOR can be used as an alternative to DAP-PDH.
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Diabetes Mellitus Tipo 2 , Pró-Fármacos , Inibidores do Transportador 2 de Sódio-Glicose , Humanos , Hipoglicemiantes/farmacocinética , Pró-Fármacos/efeitos adversos , Diabetes Mellitus Tipo 2/induzido quimicamente , Voluntários Saudáveis , Estudos Cross-Over , Inibidores do Transportador 2 de Sódio-Glicose/efeitos adversos , Equivalência Terapêutica , Formiatos , Propilenoglicóis , Área Sob a CurvaRESUMO
Temperature-dependent metalation of the new hexadentate ligand (tris(5-(pyridin-2-yl)-1H-pyrrol-2-yl)methane; H3TPM) enables the selective synthesis of both mononuclear (i.e. Na(THF)4[Fe(TPM)], kinetic product) and trinuclear (i.e. Fe3(TPM)2, thermodynamic product) complexes. Exposure of Na(THF)4[Fe(TPM)] to FeCl2 or ZnCl2 triggers cluster expansion to generate homo- or heterometallic trinuclear complexes, respectively. The developed approach enables systematic variation of ion content in isostructural metal clusters via programmed assembly.
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The syntheses, structural, and magnetic characterization of three new organometallic Ce complexes stabilized by PyCp22- (PyCp22- = [2,6-(CH2C5H3)2C5H3N]2-) are reported. Complex 1 provides the first example of a crystallographically characterized unsupported Ce-Fe bond in a molecular compound. Results from IR spectroscopy and computational analyses suggest weaker Fe â Ce electron-donation than in a previously reported Dy-Fe bonded species.
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The functionalization of UiO-67 with -NH2 groups enhances CO2 and CH4 adsorption at 1 bar and 298 K and positively influences the framework's interaction with water as evidenced by the significant enhancement of water vapour adsorption at 0.1 < P/P0 < 0.3 and 298 K.
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A microporous metal-organic framework (mIm-MOF-14) has doubly interpenetrated anionic frameworks resulting from 2-methylimidazolate linking Zn(ii) paddle-wheels of charge-neutral -type networks, and allows the inclusion of tetramethylammonium ion to exert an enhanced CO2 affinity.