A mixed chloride/trifluoromethanesulfonate ligand species in a ruthenium(II) complex

The compound [2‐(aminomethyl)pyridine‐κ²N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF₃SO₃)_0.09Cl_0.91(C₆H₈N₂)(C₁₅H₁₃N)(C₁₈H₁₅P)]CF₃SO₃·0.91CH₂Cl₂, belongs to a series of Ru^II complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [Ru^II(OTf)(ampy)(η²‐tropNH₂)(PPh₃)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH₂ is 5H‐dibenzo[a,d]cyclohepten‐5‐amine.     

Optimization of matrix solid-phase dispersion conditions for UV filters determination in biota samples

A low solvent consumption method for the determination of eight ultraviolet (UV) filters, displaying low to medium polarities, in freeze-dried samples of marine bivalves and fish is proposed. Matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometry (GC-MS) were used as sample preparation and determination techniques, respectively. This work describes the influence of several parameters (type and amount of dispersant and clean-up sorbents, as well as elution solvent) on the yield and the selectivity of the MSPD extraction. Under optimized conditions, samples (0.5?g) were ground with 2?g of Florisil in a mortar with a pestle and transferred into a polypropylene syringe, which contained 1?g of C18 as clean-up sorbent. Analytes were eluted with 5?mL of acetonitrile. This extract was concentrated to dryness, re-constituted with 1?mL of ethyl acetate and injected in the GC-MS system without any further clean-up. The global average recoveries, measured for three different biota samples, spiked at three different levels (between 50 and 1000?ng?g^?1), ranged from 80% to 101% with associated standard deviations below 10%. The inter-day precision of the method varied from 4% to 15% and the achieved LOQs (defined for a signal to noise ratio of 10) ranged from 4 to 28?ng?g^?1, referred to the freeze-dried matrix. Octocrylene (OCR) was found in some samples of fish and mussels at concentrations between 15 and 20?ng?g^?1, referred to dry mass.     

Hydroformylation and hydroalkylcarbonylation of 3,4-dihydro[2H]pyran catalysed by Co2(CO)8 under syngas conditions

In the cobalt-catalysed hydroformylation of 3,4-dihydro[2H]pyran, the influence of different reaction parameters such as time, pressure, triphenylphosphine addition, catalyst and substrate concentration has been investigated. 2-formyl-tetrahydropyran, tetrahydropyran and a hydroalkylcarbonylation product were the main reaction products. The selectivity towards 2-formyl-tetrahydropyran formation is favoured at constant catalyst and substrate concentration. The coordination of the pyran’s oxygen to the cobalt atom seems to be an important intermediate for the formation of 2-formyl-tetrahydropyran. Different substrate or catalyst concentrations promote the formation of other reduced products. The addition of triphenylphosphine to the catalyst leads to a less active species, which decreases the yield and promotes the hydroalkylcarbonylation reaction.     

In search for chelating TAMLs (tetraamido macrocyclic ligands) with peripheral bidentate donor centers: a cobalt(III) complex of the 3,3′-(2,2′-bipyridindiyl)-tailed TAML

The synthesis of 1,2-C₆H₄(NHCOCMe₂NHCO)₂-3,3′-(2,2′-bpy) (3), a TAML (tetraamido macrocyclic ligand) incorporating the peripheral 2,2′-bipyridine unit, is described. Its geometry after optimization by density functional theory (DFT) indicated a rather unfavorable conformation of four N–H amide units for forming macrocyclic transition metal complexes. This explains why the iron(III) derivative of 3 could not be obtained even after deprotonation of the N–H bonds by n-BuLi. Nevertheless, the macrocyclic complex of Co^III was synthesized in moderate yield, characterized, and explored by DFT. Our data suggest a strongly distorted square-planar geometry of the macrocyclic complex between Co^III and 3. The dihedral angle between the pyridine rings equals 80° ruling out the possibility of metal chelation by the bipyridine unit.     

A theoretical and experimental study of the racemization process of hexaaza[5]helicenes

A dynamic ¹H NMR study, together with DFT calculations, of bis-([1,2,3]triazolo)[1,5-a:5′,1′-k][1,10]phenanthroline 2 has allowed to identify the ring and open forms of a new example of ring/chain tautomerism, as well as their interconversion barriers (ring/ring and ring/open). The barrier of the exchange process between the chain forms and the ring form was found higher than the ‘racemization’ process in the closed form, so the ring opening does not contribute to the ‘racemization’. The di-1,10-methyl and di-1,10-iodo derivatives have been prepared and their properties calculated.     

Catalyst-free synthesis of 3-(alkylamino)-2-arylimidazo[1,2-a]pyridine-8-carboxylic acids via a three-component condensation

The synthesis of a number of 3-(alkylamino)-2-arylimidazo[1,2-a]pyridine-8-carboxylic acids via a facile route involving the reaction between 2-amino-3-pyridinecarboxylic acid, benzaldehyde derivatives, and isonitriles is reported. The structures of the synthesized compounds are proved by X-ray crystallography.     

Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations

Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C−H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C−B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states.