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971.
Reaction of Mo(2)Cl(4)(dppm)(2) (dppm = bis(diphenylphosphino)methane) with 6 equiv of [n-Bu(4)N][CN] or [Et(4)N][CN] in dichloromethane yields [n-Bu(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (1) and [Et(4)N](2)[Mo(2)(CN)(6)(dppm)(2)] (2), respectively. The corresponding one- and two-electron oxidation products [n-Bu(4)N][Mo(2)(CN)(6)(dppm)(2)] (3) and Mo(2)(CN)(6)(dppm)(2) (4)were prepared by reactions of 1 with the oxidant NOBF(4). Single-crystal X-ray structures of 2.2CH(3)CN, 3.2CH(3)CN.2H(2)O, and 4.2CH(3)NO(2) were performed, and the results confirmed that all three complexes contain identical ligand sets with trans dppm ligands bisecting the Mo(2)(mu-CN)(2)(CN)(4) equatorial plane. The binding of the bridging cyanide ligands is affected by the oxidation state of the dimolybdenum core as evidenced by an increase in side-on pi-bonding overlap of the mu-CN in going from 1 to 4. The greater extent of pi-donation into Mo orbitals is accompanied by a lengthening of the Mo-Mo distance (2.736(1) A in Mo(2)(II,II) (2), 2.830(1) A in Mo(2)(II,III) (3), and 2.936(1) A in Mo(2)(III,III) (4)). A computational study of the closed-shell members of this homologous series, [Mo(2)(CN)(6)(dppm)(2)](n)() (n = 2-, 0), indicates that the more pronounced side-on pi-donation evident in the X-ray structure of 4 leads to significant destabilization of the delta orbital and marginal stabilization of the delta() orbitals with respect to nearly degenerate delta and delta orbitals in the parent compound, 2. The loss of delta contributions combined with the reduced orbital overlap due to higher charges on molybdenum centers in oxidized complexes 3 and 4 is responsible for the observed increase in the length of the Mo-Mo bond. 相似文献
972.
Jack C. Kim Sang-Duk Bae Ji-A Kim Soon-Kyu Choi 《Journal of heterocyclic chemistry》1998,35(3):531-533
A Regioselective synthesis of (R)-11-hydroxyaporphine 2 directly from (R)-10,11-dihydroxyaporphine ((R)-apomorphine, 1 ) is described for the first time. The isopropylidene ketal ring of 10,11-(isopropyl-idenyldioxy)aporphine 5 obtained by the isopropylidenation of apomorphine was regioselectively opened by ten equivalents of trimethylaluminum to give (R)-10-hydroxy-11-tert-butyloxyaporphine 6 . The free 10-hydioxyl position of 6 was triflated with N-pbenyltrifluoromethanesulfonimide and potassium carbonate under reflux to give (R)-10-[(trifluoromethyl)sulfonyloxy]-11-tert-butyloxyaporphine 7 . The reduced product, 11-tert-butyloxyaporphine 8 was prepared from 7 by a palladium-catalyzed hydrogenolysis. The ether cleavage of (R)-11-tert-butyloxyaporphine with 48% hydrobromic acid afforded the desired (R)-11-hydroxyaporphine 2 in good yield. 相似文献
973.
Zh. A. Abdurakhmanova O. N. Veshkurova V. V. Kim Sh. I. Salikhov A. A. Takanaev 《Chemistry of Natural Compounds》1997,33(5):581-584
The dependence of protein kinase and RNA polymerase activities, and also of the synthesis of protein in nuclear chromatin, on the addition of benzylaminopurine and a cytokinin-binding protein to the incubation mixture has been investigated. It has been shown that all three processes are hormone-dependent. It has been found that the activity of protein kinase C is regulated by a cytokinin.A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 62 70 71. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 745–749, September–October, 1997. 相似文献
974.
钾(Ⅰ)(苯并-15-冠-5)新型配合物的合成及性质 总被引:1,自引:0,他引:1
在非水溶剂中合成并-15-冠-5与碘化钾,硫氰化钾及苦味酸钾形成的三种新型固体配合物,并进行了有关物理,化学性质表征,结果表明,钾(Ⅰ)离子不仅易苯并-15-冠-5天成常见的1:2夹心式配合物,而且还能生成稳定的1:1型固体配合物。 相似文献
975.
A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends. 相似文献
976.
The B3LYP and MP2 methods with 6-31G* basis set were used to predict the geometries of N, N-dimethylformamide (DMF) dimer and DMF–aromatic hydrocarbons interaction systems. A total of 10 conformers were obtained with
no imaginary frequencies, respectively. The interaction energies of these binary mixtures have been obtained. The analyses
of chelpg charge distribution and the atoms in molecules theory (AIM) were used to analyze the nature of the interaction.
The results show the presence of hydrogen bonds between DMF and aromatic hydrocarbons. The interaction between DMF and benzonitrile
is the strongest with the interaction energy of −21.58 kJ mol−1 (BSSE corrected), and the intensity order of interactions is DMF–benzonitrile: d2 > DMF–DMF: a2 > DMF–toluene: c1 > DMF–benzene:
b2. 相似文献
977.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
978.
Thermal properties of bio flour-filled polypropylene bio-composites with different pozzolan contents
H. -S. Kim S. -W. Choi B. -H. Lee S. Kim H. -J. Kim C. W. Cho D. Cho 《Journal of Thermal Analysis and Calorimetry》2007,89(3):821-827
In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents
were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric
curve (DTGmax) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion
of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T
g), melting temperature (T
m) and percentage of crystallinity (X
c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X
c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites
at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity
of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was
an effective method for enhancing the thermal stability and thermal expansion. 相似文献
979.
Jin‐Yu Sun Zhen Zhao Yong‐Chao Ma Miao‐Li Zhu Xiang‐Dong Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(1):m4-m6
The crystal structure of the title compound, μ‐2‐hydroxybutanedioato‐1κ2O4,O4′:2κ3O1,O2,O4‐nitrato‐2κO‐tris(1,10‐phenanthroline)‐1κ4N,N′;2κ2N,N′‐dicopper(II) nitrate tetrahydrate, [Cu2(C4H3O5)(NO3)(C12H8N2)3](NO3)·4H2O, contains an unsymmetrical dinuclear copper complex with Cu(phen)2 and Cu(phen)(NO3) moieties (phen is 1,10‐phenanthroline) bridged by a malate (2‐hydroxybutanedioate) ligand, which acts as a double‐bridging and tetradentate ligand. As a result of this double‐bridging action, especially the direct coordination of the O atom of one carboxylate group of malate to the two Cu atoms, the Cu⋯Cu distance is only 4.199 (1) Å and the two phen planes are roughly parallel [the shortest interplanar distance is 3.28 (1) Å], exhibiting an obvious intramolecular π–π stacking interaction. 相似文献
980.
甲醛与乙醛,甲醚,硝基甲烷相互作用的从头算研究 总被引:1,自引:0,他引:1
用6-31G、全构型优化,研究了甲醛与乙醛、甲醚、硝基甲烷的相互作用。结果表明所有超分子稳定构型都包含2个C—H—O氢键的平面环状结构。H—O距离为0.228~0.264 nm,作用能为—19~—24 kJ/mol,与二聚水的作用能接近。稳定性主要取决于甲基上取代基Y吸电子能力以及环状结构中氢键张力。STO-3G不很适用于研究这类分子的相互作用。 相似文献