An insight into the aromaticity of fullerene anions: experimental evidence for diamagnetic ring currents in the five-membered rings of C(60)(6-) and C(70)(6-)

Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles.     

A novel synthesis of enantiopure octahydropyrrolo[3,4-b]pyrroles by intramolecular [3 + 2] dipolar cycloaddition on chiral perhydro-1,3-benzoxazines

[reaction: see text] Condensation of N-substituted glycines with chiral 3-allyl-2-formyl perhydro-1,3-benzoxazines forms an azomethine ylide that cyclizes to give octahydropyrrolo[3,4-b]pyrrole derivatives. The [3 + 2] dipolar cycloadditions are stereoespecific leading to a single diastereoisomer. The chemical yields are dependent on the reaction temperature and the presence or absence of a base.     

Monocarbonyl cationic rhodium(I) complexes

Summary The preparations and characterisation of cationic complexes of the type [Rh(CO)(MeCN)(PR₃)₂]ClO₄, [Rh(CO)L(PR₃)₂]ClO₄ (L=py or 2-MeOpy), [Rh(CO)(L-L)(PR₃)₂]ClO₄ (L-L = bipy or phen) and [Rh(CO)(PR₃)₃]ClO₄ with PR₃ = P(p-YC₆H₄)₃ (Y=Cl, F, Me or MeO) are described.     

Heterocyclic N-glycosyl derivatives. XIV. Preparation of some N-(2,3-dideoxyglycopyranosyl)benzotriazoles by hydrogenation of N-(pent- and hex-2-enopyranosyl)benzotriazoles

Catalytic hydrogenation of a series of N-(pent- and hex-2-enopyranosyl)benzotriazoles afforded the corresponding saturated N-glycosyl derivatives having the same anomeric configuration as the starting compounds. The conformations of all compounds obtained were determined by nmr spectroscopy. The hexopyranosyl nucleosides in solution adopt the Cl conformation. On the other hand, pentopyranosyl nucleosides exist as a mixture of the two chair conformers in equilibrium, with the IC or CI ( L ) form predominating.     

Heterocyclic N-glycosyl derivatives—XIX : Glycal nucleosides. their relationship with 2',3'-unsaturated nucleosides and their utilization in the synthesis of 1',3'-two base nucleosides

The acid catalized reaction of tri-0-acetyl-D-glucal with benzotriazole or 6-methylthiopurine in acetonitrile gave a mixture of 1',2'- and 2',3'-unsaturated nucleosides, the former predominating. The relationship between these unsaturated nucleosides is studied and an allylic carbonium ion is proposed as an intermediate for these isomerizations. The acid catalized reaction of 1',2'-unsaturated nucleosides with more benzotriazole or 6-methylthiopurine gave 1',3'-two base nucleosides. The conformation and anomeric configuration of the N-glycosyl compounds obtained were assigned by NMR spectroscopy.     

The Counterion Effect on the Assembly of Coordination Networks of Cationic (η3‐Allyl)palladium Complexes Containing 3,5‐Dimethyl‐4‐nitro‐1H‐pyrazole

Two new (η³‐allyl)palladium complexes containing the ligand 3,5‐dimethyl‐4‐nitro‐1H‐pyrazole (Hdmnpz) were synthesized and characterized as [Pd(η³‐C₃H₅)(Hdmnpz)₂]BF₄ ( 1 ) and [Pd(η³‐C₃H₅)(Hdmnpz)₂]NO₃ ( 2 ). The structures of these compounds were determined by single‐crystal X‐ray diffraction to evaluate the intermolecular assembly. Each complex exhibits similar coordination behavior consistent with cationic entities comprised of two pyrazole ligands coordinated with the [Pd(η³‐C₃H₅)]⁺ fragment in an almost square‐planar coordination geometry. In 1 , the cationic entities are propagated through strong intermolecular H‐bonds formed between the pyrazole NH groups and BF ions in one‐dimensional polymer chains along the a axis. These chains are extended into two‐dimensional sheet networks via bifurcated H‐bonds. New intermolecular interactions established between NO₂ and Me substituents at the pyrazole ligand of neighboring sheets give rise to a three‐dimensional network. By contrast, compound 2 presents molecular cyclic dimers formed through N? H???O H‐bonds between two NO counterions and the pyrazole NH groups of two cationic entities. The dimers are also connected to each other through C? H???O H‐bonds between the remaining O‐atom of each NO ion and the allyl CH₂ H‐atom. Those interactions expand in a layer which lies parallel to the face (101).     

UV/Vis absorption spectroelectrochemistry of folic acid

Journal of Solid State Electrochemistry - UV/Vis absorption spectroelectrochemistry is a very promising analytical technique due to the complementary information that is simultaneously obtained...     

Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG

The new diimine fluorescent ligand ACRI‐1 based on a central acridine yellow core is reported along with its coordination complex [Co₂( ACRI‐1 )₂] ( 1 ), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to Co^II. The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), grazing incidence X‐ray diffraction (GIXRD), X‐ray absorption spectroscopy (XAS), X‐ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.     

Development of Disposable Carbon Nanofibers Electrodes Supported on Filters

The purpose of this work is to develop simple and reproducible ways to fabricate carbon nanofibers (CNFs) electrodes. Disposable CNFs electrodes were fabricated after filtering CNFs through polytetrafluoroethylene filters (PTFE), using directly as electrodes these filters with the CNFs film. The electrochemical behaviour of CNFs/PTFE electrodes were tested with ferrocenemethanol and tris(2,2′‐bypyridyl)dichlororuthenium(II) (Ru(bipy)₃²⁺). As a proof of concept of the analytical usefulness of the CNFs/PFTE electrodes, the study of vitamin B₁₂ was carried out. Multivariate calibrate has been successfully used to determine vitamin B₁₂ in a complex medium with vitamins B₁ and B₆ as interferents.