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21.
Elisa Brivio Alessandro Ceriotti Roberto Della Pergola Luigi Garlaschelli Mario Manassero Mirella Sansoni 《Journal of Cluster Science》1995,6(2):271-287
Redox condensation of [Ru3H(CO)11]- with Ni(CO)4, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRuH(CO)11)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh4][NiRu3H(CO)12] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu3, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu2 basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C
b
= 2.084 Å, Ni-C
b
= 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O
b
= 1.159 Å, M-C-O, = 176.3°,M-C--O
b
= 139.3°;other distances are: Ni-C1 = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt4]2[NiRu3(CO)12] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu3 core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C
t
= 1.878 Å, Ru-C
b
2.045 Å, Ni-C
b
= 2.055 Å, C-O
t
= 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O
b
= 138.6°; other distance is: Ni-C
t
= 1.754(10) Å,t = terminal,b = bridging. 相似文献
22.
The experimental values of the gas-phase proton affinities for a variety of 4-substituted benzonitriles, 4-substitutedN, N-dimethylanilines, and 4-substituted benzaldehydes have been examined by means of correlation analysis techniques and by ab initio quantum mechanical methods (MP2/ 6-31G(d) level). From this study it is concluded that in the gas phase, 4-(dimethylamino)-benzonitrile essentially protonates on the dimethylamino group, while protonated 4-cyanobenzaldehyde is very nearly a 21 mixture of the carbonyl- and cyano-protonated forms.This work is dedicatedin memoriam to Professor Robert W. Taft. 相似文献
23.
The new hexaalkylborazine chromium tricarbonyls (n-Pr)3B3N3Me3Cr(CO)3 (V), Me3B3N3(n-Pr)3Cr(CO)3 (VI), (i-Pr)3B3N3Me3Cr(CO)3 (VII) and Me3B3N3(i-Pr)3Cr(CO)3 (VIII) have been prepared from fac-Cr(CO)3(MeCN)3 and the corresponding borazine in dioxane or without solvent. They are much more labile than the isomeric complex Et3B3N3Et3Cr(CO)3 (IV) which can be readily obtained from Et3B3N3Me3Cr(CO)3 and Et3B3N3Et3 by ring ligand exchange. The NMR., IR., UV. and Mass spectroscopic data of the complexes IV–VIII will be briefly discussed. The preparation of the borazine derivatives (n-Pr)3B3N3Me3 (IX) and Me3B3N3(n-Pr)3 (X) is also reported. 相似文献
24.
Mario Bianchi Ugo Matteoli Piero Frediani Gloria Menchi Franco Piacenti 《Journal of organometallic chemistry》1982,236(3):375-380
Hydrogen transfer from racemic alcohols to prochiral ketones in the presence of H4Ru4(CO)8[(?)-DIOP]2 has been examined. The enantiomer-discrimination is influenced by the structure of the reactants, temperature and the excess of phosphine present. 相似文献
25.
The first total synthesis of (±)-cyclooroidin, a member of the pyrrole-imidazole alkaloid family recently isolated from the sponge Agelas oroides in optically pure form, is described. The synthesis was achieved in nine linear steps, with an overall yield of 10%. Key step was a Wolff bromoketone synthesis performed on the intermediate longamide B. 相似文献
26.
Mario Giuffrida Pietro Maravigna Giorgio Montaudo Emo Chiellini 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1643-1656
Some bipolyesters consisting of 1,2-propene glycol residue (P) and symmetric aromatic diacid residue constituted by two p-oxybenzoyl groups coupled by a terephthaloyl (HTH), phthaloyl (HOH) and isophthaloyl (HIH) group, and a nonsymmetric diacid residue constituted by a p-oxybenzoyl and a terephthaloyl group (HT), have been investigated by direct pyrolysis–mass spectrometry. The results show that intramolecular exchange reactions occurring at the pyrolysis stage cause a reorganization of the copolymer sequences. Sequential bipolyesters I–IV are ideal materials for the investigation of the extent of thermal reorganization induced in the bipolymer sequences by the pyrolytic process. 相似文献
27.
The kinetic behavior of cinnamic acids, their methyl esters, and two catechols 1-10 (ArOH) in the reaction with DPPH(*) in methanol and ethanol is not compatible with a reaction mechanism that involves hydrogen atom abstraction from the hydroxyl group of 1-10 by DPPH(*). The rate of this reaction at 25 degrees C is, in fact, comparatively fast despite that the phenolic OH group of ArOH is hydrogen bonded to solvent molecules. The observed rate constants (k(1)) relative to DPPH(*) + ArOH are 3-5 times larger for the methyl esters than for the corresponding free acids and, for the latter, decrease as their concentration is increased according to the relation k(1) = B/[ArOH](0)(m), where k(1) is given in units of M(-1) s(-1), m is ca. 0.5, and B ranges from 0.02 (p-coumaric acid) to ca. 3.48 (caffeic acid) in methanol and from 0.04 (p-coumaric acid) to ca. 13 (sinapic acid) in ethanol. Apparently, the reaction mechanism of DPPH(*) + ArOH involves a fast electron-transfer process from the phenoxide anion of 1-10 to DPPH(*). Kinetic analysis of the reaction sequence for the free acids leads to an expression for the observed rate constant, k(1), proportional to [ArOH](0)(-1/2) in excellent agreement with the experimental behavior of these phenols. The experimental results are also interpreted in terms of the influence that adventitious acids or bases present in the solvent may have. These impurities dramatically influence the ionization equilibrium of phenols and cause a reduction or an enhancement, respectively, of the measured rate constants. 相似文献
28.
Aschi M Lucente G Mazza F Mollica A Morera E Nalli M Paglialunga Paradisi M 《Organic & biomolecular chemistry》2003,1(11):1980-1988
The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a gamma-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a C(S)-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the gamma-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a gamma-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered C(alpha)-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the gamma-turn structure also in models able to adopt the beta-bend conformation. 相似文献
29.
Neira-Carrillo A Yazdani-Pedram M Retuert J Diaz-Dosque M Gallois S Arias JL 《Journal of colloid and interface science》2005,286(1):134-141
The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration. 相似文献
30.
Gancitano P Ciriminna R Testa ML Fidalgo A Ilharco LM Pagliaro M 《Organic & biomolecular chemistry》2005,3(13):2389-2392
Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis. 相似文献