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11.
An O-bonded sulphito complex, Rh(OH2)5(OSO2H)2+, is reversibly formed in the stoppedflow time scale when Rh(OH2)
6
3+
and SO2/HSO
3
−
buffer (1 <pH< 3) are allowed to react. For Rh(OH2)5OH2++ SO2 □ Rh(OH2)5(OSO2H)2+ (k1/k-1), k1 = (2.2 ±0.2) × 103 dm3 mol−1 s−1, k−1 = 0.58 ±0.16 s−1 (25°C,I = 0.5 mol dm−3). The protonated O-sulphito complex is a moderate acid (K
d
= 3 × 10−4 mol dm−3, 25°C, I= 0.5 mol dm−3). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10−3 s−1 (31°C) to Rh(OH2)4(O2SO)+ and the chelated sulphito complex takes up another HSO
3
−
in a fast equilibrium step to yield Rh(OH2)3(O2SO)(OSO2H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH2)3(O2SO)(OSO2)- → Rh(OH2)3(O2SO)(SO3)− (k
iso
= 3 × 10−4 s−1, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na4[Rh2(μ-OH)2(OH)2(μ-OS(O)O)(O2SO)(SO3) (OH2)]5H2O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water
and most organic solvents and very stable to acid-catalysed decomposition 相似文献
12.
13.
N. A. Anikin A. S. Mendkovich M. B. Kuzminskiy A. M. Andreev 《Russian Chemical Bulletin》2008,57(2):428-430
A new fast computational method for mass calculations of docking complexes by the AM1/PM3 semiempirical methods is proposed.
The computation time is shortened by at least an order of magnitude compared to alternative schemes of quantum chemical calculations.
The root-mean-square deviation of the AM1 calculated energies of formation of complexes from the results obtained by conventional
diagonalization procedure is at most 0.4 kcal mol−1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 418–420, February, 2008. 相似文献
14.
双(十二烷基亚磺酰)乙烷溶剂萃取钯及其机理的研究 总被引:2,自引:0,他引:2
本文研究用双(十二烷基亚磺酰)乙烷萃取钯的性能,在KI存在下从7mol/L盐酸介质中用含有BDSE的氯仿能定量萃取钯,有机的钯可被硫脲或氨溶液反萃继之用TMK-TritonX-100光度法测定,研究了萃取的最佳条件及干扰情况,斜率法测得萃合物组成为Pd:I:BDSE=1:2:1,红外光谱证实萃合物中BDSE的二个亚砜以硫原子与钯配位,萃合物为异位体络合物,提出了选择性萃取分离钯的新方法。 相似文献
15.
The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-2-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane. 相似文献
16.
Hidenori Hanaoka Yuka Imamoto Takahiro Hino Tetsuya Kohno Kazunori Yanagi Yoshiaki Oda 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3668-3676
Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl3(THF)3, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl3(THF)3 in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)?1 h?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (Mw = 128,700, Mw/Mn = 1.8) was obtained using a 6 ‐TIBA/B(C6F5)3 system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007 相似文献
17.
用铜(Ⅱ)—L—精氨酸配体交换薄层色谱拆分氨基酸对映体 总被引:2,自引:0,他引:2
报道了一种新的配体交换薄层色谱拆分氨基酸对映体的方法。以醋酸铜-L-精氨酸的络合物为配体交换剂,用浸渍的方法吸附在硅胶薄层板上,制成配体交换薄层,用PRISMA优化法选择出展开剂的最佳组成为:甲醇/乙腈/四氢呋喃/水=80:8.2:5.8:6,在此色谱条件下,十对氨基酸对映体得到良好的分离,D-和L-氨基酸的相对比移值在1.09-2.40之间。文中对配体交换薄层的制备方法,样品的分子结构及色谱行为 相似文献
18.
A versatile new approach for the synthesis in three steps of 2-substituted-2,3-dihydro[1,4]dioxino[2,3-b]pyridines B via a Smiles rearrangement using easily available reagents is described. A study illustrating the influence of experimental conditions on the progress of the reaction is reported. 相似文献
19.
Jun Fan Wei‐Guang Zhang Min‐Yu Tan Yu Tang Wei‐Sheng Liu Ning Tang Kai‐Bei Yu 《中国化学》2004,22(6):508-511
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes. 相似文献
20.
本文通过异氰酸酰化反应合成了含有脲基的苯乙炔新型配体及以它作为辅助配体的4′-(对甲基苯基)-6-苯基-2,2′-二联吡啶铂(II)络合物,初步研究了铂(II)络合物的光物理性质,发现由于脲基的存在,当浓度大于3.32×10-5mol/L时铂(II)络合物能够发生分子间簇集. 相似文献