The water-soluble metalloporphyrin is one of the most promising classes of compounds to be used as redox mediators/catalysts. In recent years, there has been increasing interest in the heterogeneous catalysis of metalloporphyrin, owing to the catalyst support on inorganic material not only maintain beneficial properties of catalyst, but also improve their catalytic activity and selectivity[1]. For that purpose, scientists begin to search proper support to immobilization metalloporphyrin catalysts. In general, silica, alumina, zeolite, and clay minerals were utilized as matrixes to immobilize the metalloporphyrin. 相似文献
Metallophthalocyanine (MPc) and metalloporphyrin complexes as well as some metalloproteins including myoglobin, hemoglobin, cyanocobalamin and cytochrome c catalyse the detection of nitric oxide (NO). The catalytic process often involve changes in the oxidation state of the catalyst. These complexes catalyse both the reduction and oxidation of NO. MPc complexes containing electroactive central metals such as CoPc and FePc generally show better catalytic activity towards the detection of NO than complexes containing electroinacive central metals. However, the involvement of ring based redox processes was confirmed for the homogenous NO catalysis using CoPc. 相似文献
Shape‐controlled catalysis : High‐quality Pt–Cu nanocubes with an average size of about 8 nm (see picture, scale bar=20 nm) were synthesized from a high‐temperature organic solution system in the presence of various capping ligands. These cubic Pt–Cu nanocrystals terminated with {100} facets demonstrated a superior catalytic activity towards methanol oxidation compared to similar sized Pt–Cu and Pt nanospheres.
Several catalyzed alkylation reactions of 9-methyladenine by a model [CPI, cyclopropa[c]pyrrolo[3,2-e]indol-4(5H)-one (1)] of duocarmycin anticancer drugs have been compared to the uncatalyzed reaction in gas phase and in water solvent bulk, using density functional theory at the B3LYP level with the 6-31+G(d,p) basis set and C-PCM solvation model. The effect on the CPI reactivity induced by water, formic and phosphoric acids (general acid catalysis), H3O+ (specific acid catalysis), sodium, and ammonium cation complexation (cationic catalysis) has been investigated. The calculations indicate that the specific acid catalysis and the catalysis induced by sodium cation complexation are strong in the gas phase, but solvation reduces them dramatically by electrostatic effects. The specific acid catalysis is still operative, but strongly reduced in water solution, where the reaction barrier is reduced by 8.6 kcal mol(-1) in comparison to the uncatalyzed reaction. The general acid catalysis induced by phosphoric acid (-7.3 kcal mol(-1)) and the catalysis induced by Na+ and NH4+ complexation become competitive, with a catalytic effect of -3.6 and -4.1 kcal mol(-1) in water, respectively. With the specific acid catalysis, the high acidity (low pK(a) value) of the conjugated acid of CPI (CPIH+), computed in water solution using both C-PCM (pK(a) = +2.6) and PCM-B3LYP/6-31+G(d,p) (pK(a) = +2.4) solvation models, suggests that the catalytic effects induced by NH4+ complexation could become more important than the specific acid catalysis and the general catalysis by H3PO4 under physiological conditions, due to concentration effects of the catalysts. 相似文献
The asymmetric transfer hydrogenation of aromatic ketones can be efficiently accomplished using catalysts that are based on platinum group metals which are more toxic and less abundant than iron. For that reason the discovery of iron based catalysts for the use in this transformation is important. To address this issue, we synthesized a new series of iron(II)-based precatalysts trans-[Fe(Br)(CO)(PPh(2)CH(2)CH═NCHRCHRN═CHCH(2)PPh(2))]BPh(4) (5a-5d) containing P-N-N-P ligands with the diamines (R,R)-1,2-diaminocyclohexane (a), (R,R)-1,2-diphenyl-1,2-diaminoethane (b), (R,R)-1,2-di(4-methoxyphenyl)-1,2-diaminoethane (c), and ethylenediamine (d) incorporated in the backbone using a convenient one-pot synthesis using readily available starting materials. All of the complexes, when activated with a base, show a very high activity in the transfer hydrogenation catalysis of acetophenone, using 2-propanol as a reducing agent under mild conditions. A comparison of the TOF of complexes 5a-5d show that the catalytic activity of complexes increase as the size of the substituents in the backbone of ligands increases (d < a < b = c). 相似文献
An unprecedented method that makes use of the cooperative interplay between molecular iodine and photoredox catalysis has been developed for dual light-activated intramolecular benzylic C−H amination. Iodine serves as the catalyst for the formation of a new C−N bond by activating a remote C −H bond (1,5-HAT process) under visible-light irradiation while the organic photoredox catalyst TPT effects the reoxidation of the molecular iodine catalyst. To explain the compatibility of the two involved photochemical steps, the key N−I bond activation was elucidated by computational methods. The new cooperative catalysis has important implications for the combination of non-metallic main-group catalysis with photocatalysis. 相似文献
Molecular machines? The factors involved in and the fundamental nature of a “mechanical” action within molecular catalysis is explored in detail. Such mechanical homogeneous catalysts are rare but not unknown (see graphic). The spatial and temporal nature of their catalytic action is considered. Potential implications for mimicry of enzymes are discussed.
We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one‐pot Friedel–Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin‐based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero‐Diels–Alder reaction of unactivated aldehydes with 1,3‐dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous‐like solid‐based catalysts with high catalytic performance and excellent recyclability were also constructed. 相似文献
A series of four tripodal phosphine oxide ligands, (OPR(2))(2)CHCH(2)POR(2) (1a-1d), and four mixed phosphine-phosphine oxide ligands, (OPR(2))(2)CHCH(2)PR(2) (3a-3d), were synthesized and coordinated to yttrium to produce Y(NO(3))(3)[(OPR(2))(2)CHCH(2)POR(2)] (2a-2d) and Y(NO(3))(3)[(OPR(2))(2)CHCH(2)PR(2)](OPPh(3)) (4a-4d) complexes. The previously reported ligand 1a and unknown phosphine oxide ligands 1b-1d were generated in an unprecedented trisubstitution reaction of bromoacetaldehyde diethyl acetal, while the novel partially reduced ligands 3a-3d were synthesized from 1a-1d according to a known literature protocol for the selective monoreduction of bisphosphine oxides. The neutral yttrium complexes 2a-2d are nine-coordinate and display a tricapped trigonal-prismatic geometry. Complexes 4a-4d are also neutral, nine-coordinate species and have a pendant phosphine functionality, which provides the potential to form bimetallic early-late transition-metal complexes. Additionally, yttrium complexes 2a-2d were activated with base and tested for the ring-opening polymerization of ε-caprolactone, but the results showed that base by itself was significantly more effective than the yttrium species investigated. 相似文献
The cover picture shows the structure of a Pd(II)‐enaminone complex which is prepared from Pd(OAc)2 and NH2‐featured enaminone, as well as its application in catalyzing the Suzuki‐Miyaura cross coupling reaction. As unprecedented Pd(II)‐organic species, it has been broadly used to catalyze the Suzuki‐Miyaura reaction of aryl bromides/chlorides and exhibited evidently superior catalytic activity over those commercially available Pd‐catalysts. Alongside the efficient and broad catalysis in Suzuki‐Miyaura reaction in clean aqueous medium, simply modifying reaction conditions and the enaminone structure in the Pd(II)‐enaminone complex, the homo‐coupling of aryl boronic acids can also be efficiently executed. The results disclose the application promise of enaminones in new frontiers of organometallics and catalysis. More details are discussed in the article by Wan et al. on page on page 254—258.
Hyperbranched polymers constitute a unique class of branched macromolecules, where structural complexity is complemented by relative ease of synthesis. The increasing interest in the study of these materials is due to their distinctive properties, inherently tied to their complex molecular architecture, and is augmented by the continual growth of applications like catalysis, viscosity modifiers, and sensors. We report a structural model for HBPs based on fractal scaling of both mass and connectivity. This model is shown to be of use in understanding small angle scattering data, especially in comparison with nuclear magnetic resonance spectroscopy for structural characterization.
The kinetics of the second step in the formation of a dis-azocompound from 4, 4′-bis-diazobiphenyl (bisdiazotized benzidine) with 2-naphthol-3, 6-disulfonic acid have been investigated in the presence of various concentrations of urea up to 6,6 M in aqueous buffers. The catalytic action of urea is due to a disaggregation of the diazonium ion aggregates, a base catalysis and a dielectric medium effect. 相似文献
Reaction of ethyl 3-ethoxycarbonylmethoxyfuropyridine-2-carboxylates 2a-2d with sodium ethoxide afforded 3-ethoxy derivatives 3a-3d which converted to 3-ethoxyfuropyridines 5a-5d by hydrolysis and decarboxylation of the ester group. Vilsmeier reaction of 5a and 5b gave 2-formyl-3-ethoxy derivatives 6a and 6b and 2-formyl-3-chloro derivatives 7a and 7b , while 5c and 5d did not give any formyl compound. Bromination of 3-ethoxyfuropyridines with 1 equivalent mole of bromine gave 2-bromo-3-ethoxyfuropyridines 9a-9d , whereas reaction with 3 equivalents of bromine yielded 2,2-dibromo-3,3-diethoxy-2,3-dihydrofuropyridines ( 10a and 10b ) and/or 2-bromo-3,3-diethoxy-2,3-dihydrofuropyridines 11b , 11c and 11d . Treatment of compounds 5a-5d with n-butyllithium in hexane-tetrahydrofuran at ?70° and subsequent addition of N,N-dimethylformamide yielded 2-formyl derivatives 6a-6d . 相似文献