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161.
Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands
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Dr. Mario Carrasco Irene Mendoza Dr. Eleuterio Álvarez Dr. Abdessamad Grirrane Dr. Celia Maya Dr. Riccardo Peloso Dr. Amor Rodríguez Andrés Falceto Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):410-421
To clarify the nature of the Mo?Carene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo2(Ar′)(I)(O2CR)2(OEt2)] have been prepared and characterized (Ar′=ArXyl2, R=Me; Ar′=ArMes2, R=Me; Ar′=ArXyl2, R=CF3) (Mes=mesityl; Xyl=2,6‐Me2C6H3, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe3, P(OMe)3 and PiPr3 were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN2C2Me4 (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo2(Ar′)(I)(O2CR)2( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo2(ArXyl2)(O2CMe)2(CN2C2Me4)2]I. The Mo?Carene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and Carene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules. 相似文献
162.
Dihydrogen Catalysis of the Reversible Formation and Cleavage of CH and NH Bonds of Aminopyridinate Ligands Bound to (η5‐C5Me5)IrIII
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Dr. Ana Zamorano Dr. Nuria Rendón Dr. Joaquín López‐Serrano Dr. José E. V. Valpuesta Dr. Eleuterio Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2576-2587
This study focuses on a series of cationic complexes of iridium that contain aminopyridinate (Ap) ligands bound to an (η5‐C5Me5)IrIII fragment. The new complexes have the chemical composition [Ir(Ap)(η5‐C5Me5)]+, exist in the form of two isomers ( 1+ and 2+ ) and were isolated as salts of the BArF? anion (BArF=B[3,5‐(CF3)2C6H3]4). Four Ap ligands that differ in the nature of their bulky aryl substituents at the amido nitrogen atom and pyridinic ring were employed. In the presence of H2, the electrophilicity of the IrIII centre of these complexes allows for a reversible prototropic rearrangement that changes the nature and coordination mode of the aminopyridinate ligand between the well‐known κ2‐N,N′‐bidentate binding in 1+ and the unprecedented κ‐N,η3‐pseudo‐allyl‐coordination mode in isomers 2+ through activation of a benzylic C?H bond and formal proton transfer to the amido nitrogen atom. Experimental and computational studies evidence that the overall rearrangement, which entails reversible formation and cleavage of H?H, C?H and N?H bonds, is catalysed by dihydrogen under homogeneous conditions. 相似文献
163.
A new, fused-ring oxazine was synthesized in a one-pot condensation of L-proline t-butyl ester and 1-chloroanthraquinone. The compound crystallized in space group P212121 with cell parameters a = 10.1820(10) Å, b = 15.213(2) Å, c = 18.649(2) Å, and Z = 4. The absolute structure of the compound was obtained by the Flack parameter. 相似文献
164.
The synthesis and characterization of [Zn(2)(eta(5)-C(5)Me(5))(2)], a stable molecular compound with a Zn-Zn bond and the first example of a dimetallocene structure, has opened a new chapter in the organometallic chemistry of zinc and in metallocene chemistry. The existence of two directly bonded zinc atoms demonstrates that the [Zn-Zn](2+) unit, the lightest Group 12 homologue of the well-known [Hg-Hg](2+) ion, can be stabilized by appropriate ligands. Activity in this area has increased enormously in the few years since the determination of the structure of this molecule. Numerous theoretical studies have been devoted to the investigation of the electronic, structural, and spectroscopic properties of this and related compounds, and new metal-metal coordination and organometallic compounds of zinc, cadmium, and mercury have been synthesized and structurally characterized. This Minireview gives an overview of activity in this field during the past three to four years. 相似文献
165.
María Jesús Lerma‐García Ernesto F. Simó‐Alfonso Guillermo Ramis‐Ramos José M. Herrero‐Martínez 《Electrophoresis》2008,29(22):4603-4611
A method for the determination of sterols in vegetable oils by CEC with UV–Vis detection, using methacrylate ester‐based monolithic columns, has been developed. To prepare the columns, polymerization mixtures containing monomers of different hydrophobicities were tried. The influence of composition of polymerization mixture was optimized in terms of porogenic solvent, monomers/porogens and monomer/crosslinker ratios. The composition of the mobile phase was also studied. The optimum monolith was obtained with lauryl methacrylate monomer at 60:40% (wt:wt) lauryl methacrylate/ethylene dimethacrylate ratio and 60 wt% porogens with 20 wt% of 1,4‐butanediol (12 wt% 1,4‐butanediol in the polymerization mixture). Excellent resolution between sterols was achieved in less than 7 min with an 85:10:5 v/v/v ACN–2‐propanol–water buffer containing 5 mM Tris at pH 8.0. The limits of detection were lower than 0.04 mM, and inter‐day and column‐to‐column reproducibilities at 0.75 mM were better than 6.2%. The method was applied to the determination of sterols in vegetable oils with different botanical origins and to detect olive oil adulteration with sunflower and soybean oils. 相似文献
166.
Cantó-Mirapeix A Herrero-Martínez JM Mongay-Fernández C Simó-Alfonso EF 《Electrophoresis》2008,29(18):3858-3865
Acrylate-ester-based monoliths for CEC using peroxodisulfate as a chemical initiator were prepared. The influence of two ternary porogenic solvents on the physical and chromatographic properties of butyl acrylate monolithic stationary phases was investigated. The composition and the ratio of porogenic solvent were adjusted to obtain highly permeable rigid monoliths with adequate column efficiency. Among the prepared butyl acrylate monoliths, those polymerized from a ternary porogenic solvent of acetonitrile/ethanol/water exhibited the most promising performance with a minimum plate height for naphthalene of 10.5 microm and a bed permeability of 7.3 x 10(-14) m(2). A comparison in terms of efficiency and permeability with thermal and UV initiation using alpha,alpha'-AIBN was also performed. The resulting monolithic stationary phases were evaluated in terms of reproducibility, giving RSD values below 5.1% in the electrochromatographic properties studied. 相似文献
167.
We have prepared immobilized olefins as models for the cross metathesis using different olefin partners in the presence of second generation Grubbs and Hoveyda-Grubbs precatalysts. We have demonstrated that solid-phase cross metathesis is strongly dependent on the degree of homodimerization of the non-immobilized olefin and the reactivity of such a homodimer. As in the homogeneous phase, the Hoveyda-Grubbs precatalyst was better for immobilized alpha,beta-unsaturated carbonyl compounds. 相似文献
168.
Costantino V Fattorusso E Imperatore C Mangoni A 《The Journal of organic chemistry》2008,73(16):6158-6165
Reinvestigation of the glycosphingolipid composition of the marine sponge Spheciospongia vesparia revealed the presence of vesparioside B ( 2a), a new furanose-rich hexaglycosylated glycosphingolipid that is the most complex glycosphingolipid isolated from a marine sponge to date. The structure of the new compound was elucidated using extensive 2D NMR studies and chemical degradation. Particularly useful for structure elucidation of vesparioside B was a quantum mechanical computational study, showing that in furanosides a vicinal coupling constant <2.0 Hz (for H-1/H-2 or H-3/H-4) or <3.5 Hz (for H-2/H-3) is a proof of the trans orientation of the relevant protons. This general rule, combined with ROE data, allowed us to elucidate the relative stereochemistry (including anomeric configuration) of the three furanose five-membered rings. 相似文献
169.
Ernesto Schulz Lang Gelson Manzoni de Oliveira Bárbara Tirloni Marcos Antonio Villetti 《Journal of Cluster Science》2008,19(3):459-469
(PhTe)2Hg reacts with HgCl2 and triphenylphosphine to give the clusters [(PhTe)6(Ph3P)2Hg5Cl4] · 2THF (1) and [(PhTe)8Hg6Py2Cl4] · Py (Py = pyridine) (2). In 1 each tellurium atom connects two Hg atoms, with Hg–Te distances around 2.75 Å. Phosphorus atoms of the triphenylphosphine groups complete the tetrahedral coordination of the Hg1 atoms. The second set
of Hg atoms (Hg2) is also coordinated to chlorine atoms. The three-dimensional assembling of 1 encloses circular channels with medium diameter of 12.5 Å. The cluster 2 results from substitution of the oxidized triphenylphosphine ligands of 1 by one molecule of Hg(PhTe)2 in the course of the synthetic procedures. The alternated Te–Hg bonds of 2 close a 12-membered ring with two inverted 4-membered rings in the middle. Thermogravimetrical evaluations and Raman scattering
lines of 1 and 2 are also discussed.
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Gelson Manzoni de Oliveira (Corresponding author)Email: |
170.
Sciaini G Marceca E Fernández-Prini R 《The journal of physical chemistry. B》2008,112(38):11990-11995
The existence of a charge-transfer-to-solvent process when a KI contact ion pair (CIP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as that found for the KI-CIP in supercritical ammonia (SCA); nevertheless, there are some distinct features in the two supercritical solvents. First, the effect of the solvent field due to the molecules lying beyond the first solvation shell is very different in SCW compared with that observed in SCA; in SCW it actually has a destabilizing effect over the ground and excited states. Second, our results for the thermodynamic behavior of the CIP indicate that SCA is better solvent than SCW for this species. The differences found can be attributed to the solvent molecules surrounding the CIP and bridging the two ions; they shield more efficiently the ion pair from long-range solvent effects in SCA. The different behavior is partially attributed to a stronger solvent-solvent interaction in SCW than in SCA. 相似文献