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11.
双核Salen锌配合物对含氮小分子的分子识别研究 总被引:1,自引:0,他引:1
合成并表征了由一定长度烷氧链桥连的新型双核SalenZn配合物[简记为C10-(SalenZn)2],用紫外-可见光谱滴定方法测定了主体C10-(SalenZn)2与单齿客体咪唑(Im)、吡啶(Py)、双齿客体DABCO(1,4-重氮双环[2.2.2]辛烷)及吡嗪(Pyrazine)等4种含氮客体间的轴向配位反应的配位数及缔合常数.结果表明,双核主体与咪唑、吡啶和吡嗪的配位数均为2,与DABCO的配位数为1;各主客体体系的缔合常数按K0(Im)>K0(DABCO)>K0(Pyrazine)>K0(Py)顺序递减.各主客体缔合反应的热力学参数ΔrH0m,ΔrS0m和ΔrG0m结果表明,此类识别过程均为放热和熵减少的过程.采用1HNMR方法和分子动力学构象搜索方法对主体C10-(SalenZn)2与双齿客体DABCO间的分子识别行为及产物构型作了合理解释.通过量子化学计算进一步解释了主客体识别过程中光谱性质的变化. 相似文献
12.
以PhI(OAc)2为氧化剂,考察了1,3-二烷基咪唑硫酸酯系列离子液体中Mn(Salen)催化仲醇氧化的反应. 结果表明, 在MMISM-CH2Cl2(1:4,v:v)混合溶剂中, 反应条件为n((-苯乙醇): n(醋酸碘苯): n(催化剂1c)=50: 70: 1时, (-苯乙醇的转化率可以达到97.8%, 产物苯乙酮的选择性为100%, 远高于在纯CH2Cl2中的结果, 也要好于[bmim]BF4和[bmim]PF6对该反应的促进作用. 此外, BMISM及BEISE对催化剂1c有较好的稳定作用,催化剂可以重复使用. 相似文献
13.
14.
用光谱滴定法研究了手性Salen金属配合物(SalenFe~(III), SalenCo~(II))与 四种咪唑类客体在CH_2Cl_2中的分子识别行为,发现手性Salen金属配合物与咪唑 ,N-甲基咪唑,2-甲基咪唑的配位数为2,与克霉唑的配位数为1。各识别体系缔 合常数的顺序对SalenFe~(III)为: K(Im) > K(2-MeIm) > K(N-MeIm) > K(GMZ), 对SalenCo~(II)为:K(Im) > K(2-MeIm) > K(N-MeIm)。测定的识别反应的△ _rG_m~0, △_rH_m~0, △_rS_m~0表明此类识别反应为放热、熵减少的过程,反应 体系存在焓-熵补偿关系。采用分子力学和量子化学方法进行的理论研究对实验结 果作出了合理的解释。 相似文献
15.
A comparative study of aerobic alkene epoxidations in the presence of pivalaldehyde catalyzed by the optically active Mn(III)Salen and Co(II)Salen complexes has been performed. The nature of the asymmetric induction is discussed. 相似文献
16.
Francesco P. Ballistreri Lucia Brinchi Raimondo Germani Gianfranco Savelli Gaetano A. Tomaselli Rosa M. Toscano 《Tetrahedron》2008,64(44):10239-10243
An aqueous reaction medium, based on a surfactant solution of diethyltetradecylamine N-oxide (AOE-14), was developed for the enantioselective epoxidation of 1,2-dihydronaphthalene and of various cis-β-alkyl styrenes with increasing hydrophobicity, using bleach as oxidant and the Jacobsen chiral (salen)Mn(III) as catalyst. AOE-14 is able to both solubilize all reactants in water and bind the metal of the salen complex acting as coligand. Its use leads to good yields (>75%) and to ee values ranging from 75% up to 91% even in the case of cis-β-alkyl styrenes where lower cis/trans epoxide ratios are observed. The ratio of surfactant/substrate used is 1:1 or 4:1, much lower than those generally used in the literature. 相似文献
17.
18.
Ordered, mesoporous SBA-15 functionalized with organic and inorganic moieties exhibits efficient catalytic activity in a variety
of organic transformations. In this account, reviewing our own work, three-sets of surface-modified SBA-15 materials have
been investigated. The first-set of materials consists of SBA-15 modified with organo-acidic (propyl thiol and propyl sulfonic
acid) and basic (propyl amine and propyl adenine) moieties. The second-set of materials was prepared by grafting Mn complexes
to the organo-functionalized SBA-15. The third-set composes of nanocrystalline metal oxides supported on SBA-15. All these
catalysts have been characterized by structural and spectroscopic techniques. Catalytic activities of the first-set of solid
materials have been investigated in acid/base-catalyzed reactions viz., ring-opening of epoxides with amines (producing β-amino
alcohols), esterification, three-component-Mannich reactions and cycloaddition of CO2 to epoxides. The Mn complexes grafted on organofunctionalized SBA-15 are efficient catalysts for the chemo-, regio- and stereoselective
aerial oxidation of monoterpenes at ambient conditions. TiOx, VOx, MoOx and WOx supported on SBA-15 catalyzed biomimetic oxyhalogenation of aromatic compounds. In all these reactions, the functionalized
SBA-15 showed high selectivity. 相似文献
19.
Syntheses,Structures, and Properties of Two Dicyanamide‐Bridged Polymers with a Schiff‐base Ligand
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The dicyanamide‐bridged polymers with Schiff‐base ligand, [CoNaL(dca)]n ( 1 ) and [Mn2L(dca)2]n ( 2 ) [H2L = bis(3‐methoxysalicylidene)benzene‐1,2‐diamine, dca = dicyanamide] were synthesized and characterized by elemental analyses, IR spectrroscopy and single‐crystal X‐ray diffraction. The solid‐state structures reveal that polymer 1 has double dca bridged loop‐like 1D chains, in which the heterodinuclear Co2+‐Na+ units (LCoNa) are bridged by dca with coordination mode μ1,3,5. In polymer 2 , homodinuclear Mn2+‐Mn2+(LMnMn) units are linked by dca in μ1,5‐bridging mode to form 2D planes. Magnetic susceptibility studies on 2 reveals antiferromagnetic coupling interactions between the adjacent Mn2+ ions in the LMnMn unit. 相似文献
20.
本文以聚(苯乙烯-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)为载体,对该载体进行氯甲基化、胺化修饰后与手性Salen Mn(Ⅲ)轴向配位,合成了一种新的固载型手性Salen Mn(Ⅲ)催化剂,采用FTIR,DR UV-Vis,XPS,SEM,TEM,TG等手段对催化剂进行表征.以次氯酸钠和间氯过氧苯甲酸为氧化剂,考察了固载催化剂对a-甲基苯乙烯不对称环氧化反应的催化性能,结果表明,固载型催化剂的催化活性比相应均相催化剂略低,但对映体选择性明显提高.在NaClO/PPNO氧化剂体系中0 ℃反应24h,a-甲基苯乙烯环氧化物的转化率达68%,e.e.值达99%.循环使用8次后催化效果无明显降低. 相似文献