Papers by Patricio Hermosilla-Ibáñez
Accepted Manuscripts are published online shortly after acceptance, which is prior to technical e... more Accepted Manuscripts are published online shortly after acceptance, which is prior to technical editing, formatting and proof reading. This free service from RSC Publishing allows authors to make their results available to the community, in citable form, before publication of the edited article. This Accepted Manuscript will be replaced by the edited and formatted Advance Article as soon as this is available.
European Journal of Inorganic Chemistry
Journal of Natural Products
N-Arylcytisine derivatives are quite rare. We report here a practical methodology to obtain these... more N-Arylcytisine derivatives are quite rare. We report here a practical methodology to obtain these compounds. Using the copper-catalyzed Chan-Lam coupling, we synthesized new N-arylcytisine derivatives at room temperature, in air and using inexpensive phenylboronic acids. Cytisine and 3,5-dihalocytisines can act as substrates, and among the products, the p-Br-derivative 2r was used as a substrate to obtain biaryl derivatives under Pd-coupling conditions; ester 2j was converted into its acid and amide derivatives using classical carbodiimide conditions. This shows that the Chan-Lam cross-coupling reaction can be included as a versatile synthetic tool in the derivatization of natural products.
Inorganic Chemistry Frontiers
A series of hybrid organo-inorganic mononuclear lanthanoid complexes, [n-NBu4]3[LnH(PW11O39)(phen... more A series of hybrid organo-inorganic mononuclear lanthanoid complexes, [n-NBu4]3[LnH(PW11O39)(phen)2]·H2O, denoted as LM4-1-Ln† (Ln = DyIII, TbIII, EuIII, NdIII, ErIII, HoIII and GdIII), were synthesized via hydrothermal synthesis and were structurally...
Chemical Communications
The plasticity of the coordination chemistry of lanthanoid ions has allowed the design and synthe... more The plasticity of the coordination chemistry of lanthanoid ions has allowed the design and synthesis for the first time of a family of mononuclear hybrid organic–inorganic lanthanoid complexes with slow relaxation of the magnetization.
RSC Advances
An efficient, regioselective and rapid copper-catalyzed one-pot aminoalkoxylation of styrenes has... more An efficient, regioselective and rapid copper-catalyzed one-pot aminoalkoxylation of styrenes has been developed using different alcohols and phenyl iminoiodinanes.
New Journal of Chemistry
Mixed-valence polyoxovanadates (POV) constitute a family of polyoxometalates whose electronic pro... more Mixed-valence polyoxovanadates (POV) constitute a family of polyoxometalates whose electronic properties are still unclear. Polyoxovanadoborates (POVB) a subfamily of POV, show different electronic and magnetic properties respect of those from...
Tetrahedron Letters
Abstract A copper-catalyzed radical and regioselective aminochlorination of alkenes using N -fluo... more Abstract A copper-catalyzed radical and regioselective aminochlorination of alkenes using N -fluoro-benzenesulfonimide (NFSI) and TMSCl as nitrogen and chlorine sources respectively is reported.
Molecules
Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[M... more Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[Mo6O18NC6H4N3C2H2]) (1) and a highly conjugated fluorene ([n-Bu4N]2[Mo6O18NC13H9]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.
Electrochimica Acta
Abstract CoN4 complexes like Co phthalocyanines (CoPc) have been extensively studied as electroca... more Abstract CoN4 complexes like Co phthalocyanines (CoPc) have been extensively studied as electrocatalysts for the oxygen reduction reaction (ORR) but they only promote the 2-electron reduction of O 2 to give peroxide. In contrast, vitamin B 12 a Co macrocyclic naturally occurring molecule has attracted the attention of the scientific community because instead of catalysing the 2-electron reduction of O 2 to H 2 O 2 like the other Co macrocycles it promotes the 4-electron reduction to H 2 O. Vitamin B 12 possesses an axial back ligand and this seems to be the reason for its higher activity and selectivity for the 4-electron reduction of O 2 . To test this hypothesis, we synthetized a CoPc axially coordinated to pyridine anchored to carbon nano-tubes (CoPc-Py-CNT). The Co centre is therefore coordinated to 5 N as in vitamin B 12 . The modified CoPc containing catalytic material was characterized by EPR and XPS spectroscopy. Ab initio calculations, Koutecky– Levich extrapolation and Tafel plots well describe the similarities between the 2 complexes and reveal insights into the mechanism of action of Co penta-coordinated complexes. According to our results the pyridine back ligand increases the Co-O 2 binding energy and making it more similar to that of Vitamin B 12 , favouring the splitting of the O-O bond. The back ligand then plays a crucial role in modifying Co-O 2 binding energy which is a well know reactivity descriptor.
Dalton transactions (Cambridge, England : 2003), Jan 4, 2017
The spectroscopic, electrochemical and photophysical properties of the first Re(I) organometallic... more The spectroscopic, electrochemical and photophysical properties of the first Re(I) organometallic organoimido-polyoxometalate complex [n-Bu4N][Mo6O18NC6H4-CH2-N3C2H2-Re-phen(CO)3] compared with all fragments are reported. The UV-Vis spectra are analysed using experimental and theoretical tools. In contrast to the reported studies in the literature, our results show that a new more intense band is present in the spectra of the hybrid ligand obscuring the intra-polyanion charge transfer. The electrochemical results show that the strong acceptor character of the polyoxometalate fragment is quenched by the condensation of the phenyl-triazole molecule.
ChemCatChem, 2016
The mild and fast copper‐catalyzed radical and regioselective aminoalkoxylation of styrenes by us... more The mild and fast copper‐catalyzed radical and regioselective aminoalkoxylation of styrenes by using N‐fluorobenzenesulfonimide and simple alcohols as nitrogen and alkoxy sources, respectively, was investigated. The aminoalkoxylated products obtained could be used in the synthesis of new compounds with possible activity as neurotransmitter receptor ligands.
Inorganics, 2015
This review summarizes all published data until April 2015 related to crystalline lattices formed... more This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is counterbalanced by different cations such as protonated amines, hydronium, and alkaline, and transition metal ions. The cluster is shown to form extended 1D, 2D, or 3D frameworks by forming covalent bonds or presenting hydrogen bond interactions with the present secondary cations. These cations have little influence on the solid state reflectance UV-visible spectra of the polyanionic cluster, but are shown to modify the FT-IR spectra and the magnetic behavior of the different reported species.
Crystal Growth & Design, 2015
The first borate-vacant deca-vanadoborate of formula (NH 3 CH 2 CH 2 CH 2 NH 3) 5 [(NH 3 CH 2 CH ... more The first borate-vacant deca-vanadoborate of formula (NH 3 CH 2 CH 2 CH 2 NH 3) 5 [(NH 3 CH 2 CH 2 CH 2 NH 3)V 10 B 24 O 66 H 8 ]•13.23H 2 O with an occluded 1,3-propanediammonium cation, using molten methylboronic acid flux reaction is reported. This cluster lacks four borate units with respect to all known deca-vanadoborates. It crystallizes in the orthorhombic P2 1 2 1 2 space group which is non-centrosymmetric, leading to the first non-centrosymmetric deca-vanadoborate reported in the literature. Even though the decavanadoborates formed by 28 borate units have an inner space large enough to host a molecule, no examples have been reported before. The electronic properties were studied using electronic spectroscopy, corroborating a fully reduced species, due to the lack of intervalence charge transfer transitions in the 1000 to 1500 nm region. The magnetic behavior provided evidence that the studied cluster presents strong antiferromagnetism among the ten V IV spincarriers, with an S = 0 ground state. Using a model considering three different exchange pathways, three different J values were obtained, all of them antiferromagnetic in nature.
Acta Crystallographica Section C-crystal Structure Communications, 2006
In the title monomer, [Cu(NO3)2(C24H16N2)2], the copper(II) cation is eight-coordinate within an ... more In the title monomer, [Cu(NO3)2(C24H16N2)2], the copper(II) cation is eight-coordinate within an octahedral-like polyhedron. The coordination polyhedron is formed by two chelating diphenylphenanthroline groups that define the highly distorted CuN4 equatorial plane and two weakly bound bidentate (chelating) nitrate groups in the apical or axial positions. The complex crystallizes in the monoclinic space group C2/c; a twofold axis passes through the copper(II) cation and bisects the two nitrate ligands. This gives the molecule C2 point-group symmetry, rendering only half of the molecule independent.
Acta Crystallographica Section C-crystal Structure Communications, 2007
Two polymorphic forms of a mixed zinc/copper biquinoline dihydrogenphosphate are presented, showi... more Two polymorphic forms of a mixed zinc/copper biquinoline dihydrogenphosphate are presented, showing almost identical monomeric units, viz. (2,2'-biquinoline-kappa(2)N,N')bis(dihydrogenphosphato-kappaO)copper(II)/zinc(II), formulated as [Zn(x)Cu(1-x)(H(2)PO(4))(2)(C(18)H(12)N(2))], with x = 0.88 (1) and 0.90 (2). The cation is tetrahedrally coordinated to a chelating biquinoline system and two diprotonated phosphate anions. The structures differ mainly in their intermolecular hydrogen-bonding interactions, leading to different packing schemes. No significant evidence of stress due to the Zn/Cu solid solution formation was detected.
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Papers by Patricio Hermosilla-Ibáñez