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41.
Two new classes of proline‐based P,O and P,N ligands were prepared and applied in the iridium‐catalyzed asymmetric hydrogenation of alkenes. Both types of ligands induced high enantioselectivities in the hydrogenation of trisubstituted C?C bonds. Iridium complexes derived from P,O ligands bearing sterically demanding amide or urea groups at the pyrrolidine N‐atom proved to be especially efficient catalysts for the conjugate reduction of α,β‐unsaturated esters and ketones, whereas analogous P,N ligands led to better results with dialkyl‐phenyl‐substituted alkenes and an allylic alcohol as substrates. 相似文献
42.
碳纳米管担载纳米Ir催化生物质基乙酰丙酸合成γ-戊内酯 总被引:1,自引:0,他引:1
以碳纳米管(CNTs)担载Ir纳米粒子为催化剂进行生物质基平台化合物乙酰丙酸(LA)选择加氢制备γ-戊内酯(GVL)的研究,并利用X射线衍射、X射线光电子能谱和透射电镜表征了使用前后的Ir/CNT催化剂,探讨了影响LA催化加氢制GVL反应性能的因素和该反应的可能路径.结果表明,与Ru,Rh和Pd等传统铂族金属相比,Ir/CNT催化剂不但可在温和条件下(50℃,2.0 MPa,H2)实现LA至GVL的完全转化,且可对多类直接源于生物质水解的含等量LA/甲酸的“真实”体系实现GVL的高效选择合成. 相似文献
43.
Alberto Ceccon Annalisa Bisello Laura Crociani Alessandro Gambaro Paolo Ganis Francesco Manoli Saverio Santi Alfonso Venzo 《Journal of organometallic chemistry》2000,600(1-2):94-111
The Rh(COD) and Ir(COD) homobimetallic complexes of s-indacene-diide, 2,6-dimethyl-s-indacene-diide, as-indacene-diide, and 2,7-dimethyl-as-indacene-diide have been synthesized from the di-lithium salts of the dianions and metal dimers [M(μ-Cl)L2]2 (M = Rh, Ir; L2 = COD, NBD, (ethylene)2, (CO)2 as mixtures of syn and anti isomers. The syn/anti ratio depends on the nature of the ancillary ligands at the metal and on the s or as geometry of the bridging ligand. In the reaction of the 2,7-dimethyl-as-indacene-diide-[M(COD)]2 species with CO, the higher reactivity of the syn isomers has been justified on the basis of a greater instability of the ground state due to steric interactions between the COD groups. Bis-η1 metal-bonded intermediates have been identified in the carbonylation of iridium derivatives; on the other hand, the formation of the bis-η5 mixed complexes syn and anti-{2,7-dimethyl-as-indacene-diide-[Rh(COD)][Rh(CO)2]} and their reactivity strongly support the existence of metal---metal interaction in the rhodium derivatives. 相似文献
44.
基于以H3PO4为反应介质,用HAc-NaAc(1+8)(pH5.7)作缓冲溶液,在沸水浴中加热条件下,痕量铱(Ⅳ)能灵敏地催化高碘酸钾氧化甲基绿的褪色反应,建立了一种测定痕量铱(Ⅳ)的新催化光度法。研究了反应的最佳条件。催化反应吸光度A与非催化反应吸光度A0的差值ΔA与铱(Ⅳ)的质量浓度ρ在0~2.0μg/25mL范围内呈良好的线性关系。检出限为2.97×10-10g/mL。对1μg/25mL铱(Ⅳ)测定的相对标准偏差为1.7%(n=11)。测定了动力学参数。该催化反应对铱(Ⅳ)为一级反应,总反应为准一级反应。反应的表观速率常数为4.613×10-4/s,表观活化能为40.56kJ/mol。该方法用于分子筛样品和活性炭中痕量铱(Ⅳ)的测定,回收率97.9%~104.4%。 相似文献
45.
New sensing films have been developed for the detection of molecular oxygen. These films are based on luminescent Ir(III) dyes incorporated either into polystyrene (with and without plasticizer) or metal oxide, nanostructured material. The preparation and characterization of each film have been investigated in detail. Due to their high sensitivity for low oxygen concentration, the parameters pO2(S=1/2) and ΔI1% have been also evaluated in order to establish the most sensitive membrane for controlling concentrations between 0 and 10% and low oxygen concentrations (lower than 1%), respectively. The results show that the use of nanostructured material increased the sensitivity of the film; the most sensitive membrane for controlling O2 between 0 and 10% is based on N1001 immobilized in AP200/19 (ksv = 2848 ± 101 bar−1 and pO2(S=1/2)=0.0006), and the complex N969 incorporated into AP200/19 seems to be the most suitable for applications in oxygen trace sensing (ΔI1% = 93.13 ± 0.13%). 相似文献
46.
Mahendra Yadav 《Journal of organometallic chemistry》2010,695(6):841-763
The meso-pyridyl substituted dipyrromethane ligands 5-(4-pyridyl)dipyrromethane (4-dpmane) and 5-(3-pyridyl)dipyrromethane (3-dpmane) have been employed in the synthesis of a series of complexes with the general formulations [(η6-arene)RuCl2(L)] (η6-arene = C6H6, C10H14) and [(η5-C5Me5)MCl2(L)] (M = Rh, Ir). The reaction products have been characterized by microanalyses and spectral studies and molecular structures of the complexes [(η6-C10H14)RuCl2(4-dpmane)] and [(η5-C5Me5)IrCl2(3-dpmane)] have been determined crystallographically. For comparative studies, geometrical optimization have been performed on the complex [(η5-C5Me5)IrCl2(4-dpmane)] using exchange correlation functional B3LYP. Optimized bond length and angles are in good agreement with the structural data of the complex [(η5-C5Me5)IrCl2(3-dpmane)]. The complexes [(η6-C10H14)RuCl2(3-dpmane)], [(η5-C5Me5)RhCl2(3-dpmane)] and [(η5-C5Me5)IrCl2(3-dpmane)] have been employed as a transfer hydrogenation catalyst in the reduction of aldehydes. It was observed that the rhodium and iridium complexes mentioned above are more effective in this regard in comparison to the ruthenium complex. 相似文献
47.
Reaction of the benzene-linked bis(pyrazolyl)methane ligands, 1,4-bis{bis(pyrazolyl)-methyl}benzene (L1) and 1,4-bis{bis(3-methylpyrazolyl)methyl}benzene (L2), with pentamethylcyclopentadienyl rhodium and iridium complexes [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh and Ir) in the presence of NH4PF6 results under stoichiometric control in both, mono and dinuclear complexes, [(η5-C5Me5)RhCl(L)]+ {L = L1 (1); L2 (2)}, [(η5-C5Me5)IrCl(L)]+ {L = L1 (3); L2 (4)} and [{(η5-C5Me5)RhCl}2(μ-L)]2+ {L = L1 (5); L2 (6)}, [{(η5-C5Me5)IrCl}2(μ-L)]2+ {L = L1 (7); L2 (8)}. In contrast, reaction of arene ruthenium complexes [(η6arene)Ru(μ-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6) with the same ligands (L1 or L2) gives only the dinuclear complexes [{(η6-C6H6)RuCl}2(μ-L)]2+ {L = L1 (9); L2 (10)}, [{(η6-p-iPrC6H4Me)RuCl}2(μ-L)]2+ {L = L1 (11); L2 (12)} and [{(η6-C6Me6)RuCl}2(μ-L)]2+ {L = L1 (13); L2 (14)}. All complexes were isolated as their hexafluorophosphate salts. The single-crystal X-ray crystal structure analyses of [7](PF6)2, [9](PF6)2 and [11](PF6)2 reveal a typical piano-stool geometry around the metal centers with six-membered metallo-cycle in which the 1,4-bis{bis(pyrazolyl)-methyl}benzene acts as a bis-bidentate chelating ligand. 相似文献
48.
Iridium oxide nanoparticles are grown on a glassy carbon electrode by electrodepositing method. The electrochemical behavior and electrocatalytic activity of modified electrode towards reduction of iodate and periodate are studied. The reductions of both ions occur at the unusual positive peak potential of 0.7 V vs. reference electrode. The modified electrode is employed successfully for iodate and periodates detection using cyclic voltammetry, hydrodynamic amperometry and flow injection analysis (FIA). In the performed experiments, flow injection amperometric determination of iodate and periodate yielded calibration curves with the following characteristics: linear dynamic range up to 100 and 80 μM, sensitivity of 140.9 and 150.6 nA μM−1 and detection limits of 5 and 36 nM, respectively. The repeatability of the modified electrode for 21 injections of 1.5 μM of iodate solution is 1.5%. The interference effects of NO2−, NO3−, ClO3−, BrO3−, ClO4−, SO42−, Cu2+, Zn2+, Mn2+, Mg2+, Cd2+, Ca2+, Na+, K+, NH4+ and K+, CH3COO− and glucose were negligible at the concentration ratio of more than 1000. The obtained attractive analytical performance together with high selectivity and simplicity of the proposed method provide an effective and e novel modified electrode to develop an iodate and periodate sensor. Sensitivity, selectivity, the liner concentration range and the detection limit of the developed sensor are all much better than all known similar sensors in the literature for iodate and periodate determination. 相似文献
49.
50.
应用激光解吸电离飞行时间质谱对几种不同结构的吡嗪稠环齐聚物进行了表征.样品溶解在二甲基亚砜中,以正离子方式记录谱图,结果发现除了产生目标化合物的质子化的分子离子峰外,还产生了少量的碎片分子离子峰.结果表明激光解吸电离飞行时间质谱能有效地、快速准确地给出这类化合物的分子离子峰,为吡嗪类稠环齐聚物的研究提供了有效的表征方法. 相似文献