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81.
Kryatov SV Chavez FA Reynolds AM Rybak-Akimova EV Que L Tolman WB 《Inorganic chemistry》2004,43(6):2141-2150
Dioxygen activation by enzymes such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases occurs at a nonheme diiron active site supported by two histidines and four carboxylates, typically involving a (peroxo)diiron(III,III) intermediate in an early step of the catalytic cycle. Biomimetic tetracarboxylatodiiron(II,II) complexes with the familiar "paddlewheel" topology comprising sterically bulky o-dixylylbenzoate ligands with pyridine, 1-methylimidazole, or THF at apical sites readily react with O(2) to afford thermally labile peroxo intermediates that can be trapped and characterized spectroscopically at low temperatures (193 K). Cryogenic stopped-flow kinetic analysis of O(2) adduct formation carried out for the three complexes reveals that dioxygen binds to the diiron(II,II) center with concentration dependences and activation parameters indicative of a direct associative pathway. The pyridine and 1-methylimidazole intermediates decay by self-decomposition. However, the THF intermediate decays much faster by oxygen transfer to added PPh(3), the kinetics of which has been studied with double mixing experiments in a cryogenic stopped-flow apparatus. The results show that the decay of the THF intermediate is kinetically controlled by the dissociation of a THF ligand, a conclusion supported by the observation of saturation kinetic behavior with respect to PPh(3), inhibition by added THF, and invariant saturation rate constants for the oxidation of various phosphines. It is proposed that the proximity of the reducing substrate to the peroxide ligand on the diiron coordination sphere facilitates the oxygen-atom transfer. This unique investigation of the reaction of an O(2) adduct of a biomimetic tetracarboxylatodiiron(II,II) complex provides a synthetic precedent for understanding the electrophilic reactivity of like adducts in the active sties of nonheme diiron enzymes. 相似文献
82.
Zoya A. Solodovnikova Sergey F. Solodovnikov 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(7):i53-i56
The crystal structures of dirubidium heptaoxodimolybdate, Rb2Mo2O7, and dicaesium heptaoxodimolybdate, Cs2Mo2O7, in the space groups Ama2 and P21/c, respectively, have been determined for the first time by single‐crystal X‐ray diffraction. The structures represent two novel structure types of monovalent ion dimolybdates, A2Mo2O7 (A = alkaline elements, NH4, Ag or Tl). In the structure of Rb2Mo2O7, Mo atoms are on a twofold axis, on a mirror plane and in a general position. One of the Rb atoms lies on a twofold axis, while three others are on mirror planes. Two O atoms attached to the Mo atom on a mirror plane are located on the same plane. Rubidium dimolybdate contains a new kind of infinite Mo–O chain formed from linked MoO4 tetrahedra and MoO6 octahedra alternating along the a axis, with two terminal MoO4 tetrahedra sharing corners with each octahedron. The chains stack in the [001] direction to form channels of an approximately square section filled by ten‐coordinate Rb ions. Seven‐ and eight‐coordinate Rb atoms are located between chains connected by a c translation. In the structure of Cs2Mo2O7, all atoms are in general positions. The MoO6 octahedra share opposite corners to form separate infinite chains running along the c axis and strengthened by bridging MoO4 tetrahedra. The same Mo–O polyhedral chain occurs in the structure of Na2Mo2O7. Eight‐ to eleven‐coordinate Cs atoms fill the space between the chains. The atomic arrangement of caesium dimolybdate has an orthorhombic pseudosymmetry that suggests a possible phase transition P21/c→Pbca at elevated temperatures. 相似文献
83.
de Meijere A Kozhushkov SI Rauch K Schill H Verevkin SP Kümmerlin M Beckhaus HD Rüchardt C Yufit DS 《Journal of the American Chemical Society》2003,125(49):15110-15113
The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners. 相似文献
84.
Jussila T Tkachenko NV Parkkinen S Lemmetyinen H 《Journal of photochemistry and photobiology. B, Biology》2001,62(3):128-132
Kinetics of the photo-induced processes of the transient states of the 3,4-didehydroretinal (3,4-dhr) modified bacteriorhodopsin (bR) was studied by a flash photolysis method in a water suspension at room temperature. The excitation initiated a photocycle with several transient intermediates similar to the trans photocycle of native bR. The main observation of the study was that although major part (80%) of the population of the M state relaxed via the O intermediate as in natural bR, 20% relaxed directly to the bR ground state in 200 ms. 相似文献
85.
The [Au2(TeSe2)2]2- anion has been prepared from the reaction of [TeSe3]2- with AuCN in DMF in the presence of PEt3 and from the reaction of [TeSe2]2- with AuCN in DMF. Reaction of [TeSe2]2- with AuCN in DMF in the presence of PEt3 leads ultimately to the [Au2(Te2)2]2- anion. 相似文献
86.
V. Ya. Kavun N. A. Didenko A. B. Slobodyuk I. A. Tkachenko A. V. Gerasimenko N. F. Uvarov V. I. Sergienko 《Journal of Structural Chemistry》2005,46(5):839-847
The mobility of fluoride and ammonium ions (180–480 K) in compounds K2? n (NH4)nZrF6 (0.2 ≤ n ≤ 1.70) was investigated by 19F and 1H NMR. Correlations have been found between the composition of the cation sublattice, the character of ion motions, and phase transition temperature in these compounds. The hightemperature modifications with n ≥ 0.85 of the compounds are characterized by translational diffusion of fluoride and ammonium ions and by uniaxial anisotropy of the 19F magnetic shielding tensor. The electrophysical characteristics of these compounds were studied in the temperature range 300–480 K. 相似文献
87.
Alexander V. Virovets Sergey N. Konchenko 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(9):e383-e384
The structure of the title compound, hexacarbonyl‐1κ3C,2κ3C‐[3(η5)‐cyclopentadienyl]bis(μ3‐selenido)diiron(II)cobalt(II),[CoFe2(μ3‐Se)2(C5H5)(CO)6], was redetermined at room temperature and the correct C2/c space group was assumed instead of the previously reported P space group [Mathur et al. (1995). Organometallics, 14 , 2115–2118]. Analysis of the literature data showed that the previously reported triclinic parameters correspond to a primitive subcell of the actual monoclinic C‐centred cell with cell dimensions close to those found by us. The title compound appeared to be isostructural with the sulfur–selenium analogue. 相似文献
88.
Bakhmutov VI Berry JF Cotton FA Ibragimov S Murillo CA 《Dalton transactions (Cambridge, England : 2003)》2005,(11):1989-1992
Reaction of activated palladium metal with a HNO3/acetic acid mixture produces both orange Pd3(OAc)6, 1, and purple Pd3(OAc)5(NO2), 2. Compound has a trinuclear structure derived from that of the well-known triangular complex 1 in which one acetate group has been replaced by a nitrite group which is bonded to one palladium atom by the nitrogen atom and to another Pd atom using one of the oxygen atoms. Highly pure 1 can be made by continuous removal of the nitric oxides from the reaction mixture using a flow of N2. 1H NMR spectra of solutions of 1 in CDCl3 and C6D6 show several signals of various intensities when a small amount of water is present in the deuterated solvents but only one signal when the solvents are thoroughly dried. These results are consistent with the occurrence of one or more hydrolysis processes when the solvents contain water and suggest that hypotheses about various [Pd(OAc)2]n aggregates that have previously been brought forward in the literature to explain the complexity of the spectrum of 1 are unnecessary, especially for nonpolar solvents. Compound 2 does not hydrolyze, and in wet or dried solvents shows a 1H NMR spectrum that consists of five equal-intensity signals due to the five nonequivalent acetate groups. 相似文献
89.
Valentine G. Nenajdenko Sergey V. Druzhinin Elizabeth S. Balenkova 《Tetrahedron letters》2005,46(51):8853-8855
Reactions of α,β-unsaturated CF3-ketones with nitromethane and ethyl nitroacetate have been investigated. We found that α,β-unsaturated trifluoromethylketones react with ethyl nitroacetate in the presence of calcinated potassium fluoride to form two classes of 1,4-conjugated addition products: CF3-γ-nitroketones and 6,6,6-trifluoro-2-nitro-5-oxohexanoates in nearly quantitative yields. The products obtained are precursors for CF3-pyrrolidine synthesis. 相似文献
90.
Jones NA Nepogodiev SA MacDonald CJ Hughes DL Field RA 《The Journal of organic chemistry》2005,70(21):8556-8559
Described herein is the synthesis of 3-C-carboxy-5-deoxy-L-xylose (aceric acid), a rare branched-chain sugar found in the complex pectic polysaccharide rhamnogalacturonan-II. The key synthetic step in the construction of aceric acid was the stereoselective addition of 2-trimethylsilyl thiazole to 5-deoxy-1,2-O-isopropylidene-alpha-L-erythro-pentofuran-3-ulose (2), which was prepared from L-xylose. The thiazole group was efficiently converted into the required carboxyl group via conventional transformations. Aceric acid was also synthesized by dihydroxylation of a 3-C-methylene derivative of 2 followed by oxidation of the resulting hydroxylmethyl group. The C-2 epimer of aceric acid was also synthesized using thiazole addition chemistry, starting from L-arabinose. 相似文献