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1.
Molecular Design and Syntheses of Tetracyano‐5,10‐porphyrinquinodimethane Showing Stabilized LUMO
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Ken‐ichi Yamashita Shino Sakamoto Akihiro Suzuki Prof. Ken‐ichi Sugiura 《化学:亚洲杂志》2016,11(7):1004-1007
An isomer of tetracyanoporphyrinquinodimethane (TCPQ), 5,10‐TCPQ, was designed, synthesized, and structurally characterized, and its basic properties were discussed with emphasis on comparison with those of reported 5,15‐TCPQ. The title compound was synthesized by a convenient cascade reaction involving a catalyst‐free aromatic nucleophilic substitution reaction and the Uno–Takahashi reaction. The obtained π‐expanded redox molecule acted as a Wurster‐type redox molecule that underwent not only reduction but also oxidation processes. Furthermore, its absorption spectrum showed a large bathochromic shift that extended to the near‐IR region, approximately 1150 nm. 相似文献
2.
Dibyendu Bhattacharya Che‐Hao Chang Yu‐Hsiang Cheng Long‐Li Lai Hsiu‐Yu Lu Ching‐Yao Lin Kuang‐Lieh Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(17):5275-5283
Self‐assembled, hexarhenium(I), triangular metalloprism compound [{(CO)3Re(μ‐ 2 )Re(CO)3}3(μ3‐ 1 )2] ( 3 ) featuring three bis‐chelating pillarlike indigo dianions (μ‐ 2 ), each of which connects two fac‐Re(CO)3 cores, which are interconnected by a tritopic N donor, that is, a 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (μ3‐ 1 , tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near‐infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3 n species, where n=3+, 0, 3?, 4?, 5?, 8?, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin‐layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site‐specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with μ‐ 2 or μ3‐ 1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei (185,187Re, I=5/2) in the reduced intermediates. The framework has C2 symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure‐based DFT confirm that the triply degenerate HOMO has ≥70 % indigo character with a sizable dπ‐Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2′‐bis‐benzimidazolate‐ (BiBzlm) or alkoxy‐pillared ReI metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N? to N,O?. 相似文献
3.
Radovan Bast Dr. Andreas Heßelmann Dr. Paweł Sałek Dr. Trygve Helgaker Prof. Dr. Trond Saue Dr. 《Chemphyschem》2008,9(3):445-453
We test the performance of four‐component relativistic density functional theory by calculating the static and frequency‐dependent electric dipole–dipole polarizabilities of all (ground‐state) closed‐shell atoms up to Ra. We consider 12 nonrelativistic functionals, including three asymptotically shape‐corrected functionals, by using two smooth interpolation schemes introduced by the Baerends group: the gradient‐regulated asymptotic connection (GRAC) procedure and the statistical averaging of (model) orbital potentials (SAOP). Basis sets of doubly augmented triple‐zeta quality are used. The results are compared to experimental data or to accurate ab initio results. The reference static electric dipole polarizability of palladium has been obtained by finite‐field calculations using the coupled‐cluster singles, doubles, and perturbative triples method within this work. The best overall performance is obtained using hybrid functionals and their GRAC shape‐corrected versions. The performance of SAOP is among the best for nonhybrid functionals for Group 18 atoms but its precision degrades when considering the full set of atoms. In general, we find that conclusions based on results obtained for the rare‐gas atoms are not necessarily representative of the complete set of atoms. GRAC cannot be used with effective core potentials since the asymptotic correction is switched on in the core region. 相似文献
4.
Dipl.‐Ing. Wilhelm Sicking Priv.‐Doz. Dr. Holger Somnitz Prof. Dr. Carsten Schmuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(35):10937-10948
The mammalian heme enzyme myeloperoxidase (MPO) catalyzes the reaction of Cl? to the antimicrobial‐effective molecule HOCl. During the catalytic cycle, a reactive intermediate “Compound I” (Cpd I) is generated. Cpd I has the ability to destroy the enzyme. Indeed, in the absence of any substrate, Cpd I decays with a half‐life of 100 ms to an intermediate called Compound II (Cpd II), which is typically the one‐electron reduced Cpd I. However, the nature of Cpd II, its spectroscopic properties, and the source of the additional electron are only poorly understood. On the basis of DFT and time‐dependent (TD)‐DFT quantum chemical calculations at the PBE0/6‐31G* level, we propose an extended mechanism involving a new intermediate, which allows MPO to protect itself from self‐oxidation or self‐destruction during the catalytic cycle. Because of its similarity in electronic structure to Cpd II, we named this intermediate Cpd II′. However, the suggested mechanism and our proposed functional structure of Cpd II′ are based on the hypothesis that the heme is reduced by charge separation caused by reaction with a water molecule, and not, as is normally assumed, by the transfer of an electron. In the course of this investigation, we found a second intermediate, the reduced enzyme, towards which the new mechanism is equally transferable. In analogy to Cpd II′, we named it FeII′. The proposed new intermediates Cpd II′ and FeII′ allow the experimental findings, which have been well documented in the literature for decades but not so far understood, to be explained for the first time. These encompass a) the spontaneous decay of Cpd I, b) the unusual (chlorin‐like) UV/Vis, circular dichroism (CD), and resonance Raman spectra, c) the inability of reduced MPO to bind CO, d) the fact that MPO‐Cpd II reduces SCN? but not Cl?, and e) the experimentally observed auto‐oxidation/auto‐reduction features of the enzyme. Our new mechanism is also transferable to cytochromes, and could well be viable for heme enzymes in general. 相似文献
5.
A DFT Study of Tungsten–Methylidene Formation on a W/ZSM‐5 Zeolite: The Metathesis Active Site
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Dr. Thana Maihom Prof. Dr. Michael Probst Prof. Dr. Jumras Limtrakul 《Chemphyschem》2015,16(15):3334-3339
Tungsten–methylidene formation from ethene on either the WIV, WV, or WVI active sites of a W/ZSM‐5 zeolite is investigated by using the M06‐L functional. The reaction is assumed to proceed in two steps; the first step is the [2+2] cycloaddition between ethene and the W?O active site to form an oxametallacycle intermediate. The intermediate is then decomposed to produce the W–methylidene active site from the metathesis reaction. The overall activation barrier of the reaction on WVI (27.3 kcal mol?1) is considerably lower than the ones for WIV and WV (69.4 and 37.1 kcal mol?1, respectively). Moreover, the reaction involving the WVI site also stabilizes intermediates and products to a larger extent than the ones on the WIV and WV sites. As a result, we have demonstrated that the reaction of the W–methylidene metathesis active site is both kinetically and thermodynamically favored to occur on the WVI active site of the zeolite. 相似文献
6.
Reduction Process of Tetraplatin in the Presence of Deoxyguanosine Monophosphate (dGMP): A Computational DFT Study
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Filip Šebesta Prof. Dr. Jaroslav V. Burda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):1037-1047
The reduction mechanism of [PtIV(dach)Cl4] (dach=diaminocyclohexyl) in the presence of dGMP was studied. The first step is substitution of a chloro ligand by dGMP, followed by nucleophilic attack of a phosphate or sugar oxygen atom to the C8‐position of guanine. Subsequent reduction forms the [PtII(dach)Cl2] complex. The whole process is completed by a hydrolysis. Two different pathways for the substitution reaction were examined: a direct associative and a Basolo–Pearson autocatalytic mechanism. All the explored structures were optimized at the B3LYP‐D3/6‐31G(d) level and by using the COSMO solvation model with Klamt's radii. Single‐point energetics was determined at the B3LYP‐GD3BJ/6‐311++G(2df,2pd)/PCM/scaled‐UAKS level. Activation barriers were used for an estimation of the rate constants and these were compared with experimental values. It was found that the rate‐determining step is the nucleophilic attack with a slightly faster performance in the 3′‐dGMP branch than in the case of 5′‐dGMP with activation barriers of 21.1 and 20.4 kcal mol?1 (experimental: 23.8 and 23.2 kcal mol?1). The reduction reaction is connected with an electron flow from guanine. The product of the reduction reaction is a chelate structure, which dissociates within the last reaction step, that is, a hydrolysis reaction. The whole redox process (substitution, reduction, and hydrolysis) is exergonic by 34 and 28 kcal mol?1 for 5′‐dGMP and 3′‐dGMP, respectively. 相似文献
7.
A Time‐Dependent DFT Study of the Absorption and Fluorescence Properties of Graphene Quantum Dots
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Meilian Zhao Feng Yang Prof. Ying Xue Prof. Dan Xiao Prof. Yong Guo 《Chemphyschem》2014,15(5):950-957
Absorption and fluorescence spectra of graphene quantum dots (GQDs) have been computed by using time‐dependent density functional theory (TDDFT). Different functionals, including PBE, TPSSh, B3LYP, PBE0, CAM‐B3LYP, and LC‐ωPBE, have been tested and B3LYP/6‐31G(d) has been proven to be the most accurate method for our work. The bulk solvent effects of toluene and dichloromethane have been assessed by using the polarizable continuum model (PCM). The absorption wavelength of GQDs in solvents is red‐shifted compared with that in the gas phase. Edge functionalization effects analysis shows that a small number of substituted groups on GQDs induce a small redshift whereas a large redshift occurs when the edges of GQDs are all decorated. Little difference in the fluorescent emission was observed in solvents and in the gas phase. Molecular orbital transition and transition density matrix analysis have been performed. The electronic transition mainly occurs in the middle part of the structure of C132. The strong absorption of C132 corresponds to a S0→S3 transition and the fluorescence emission is ascribed to a S1→S0 transition, which indicates that Kasha’s rule is obeyed. 相似文献
8.
Redox‐Active‐Ligand‐Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands
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Dr. Bidraha Bagh Daniël L. J. Broere Dr. Maxime A. Siegler Dr. Ir. Jarl Ivar van der Vlugt 《Angewandte Chemie (International ed. in English)》2016,55(29):8381-8385
Coordination of a redox‐active pyridine aminophenol ligand to RuII followed by aerobic oxidation generates two diamagnetic RuIII species [ 1 a (cis) and 1 b (trans)] with ligand‐centered radicals. The reaction of 1 a / 1 b with excess NaN3 under inert atmosphere resulted in the formation of a rare bis(nitrido)‐bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru‐N‐Ru fragments. The spontaneous reduction of the ligand centered radical in the parent 1 a / 1 b supports the oxidation of a nitride (N3?) to half an equivalent of N2. The trinuclear omplex is reactive toward TEMPO‐H, tin hydrides, thiols, and dihydrogen. 相似文献
9.
10.
Justin A. Bogart Connor A. Lippincott Dr. Patrick J. Carroll Dr. Corwin H. Booth Prof. Eric J. Schelter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17850-17859
Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2‐tBuNOH)C6H4CH2)3N]3? (TriNOx3?), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNOx)thf][BArF4], in which ArF=3,5‐(CF3)2‐C6H3, and [Ce(TriNOx)py][OTf]. A rare complete Ce–halide series, Ce(TriNOx)X, in which X=F?, Cl?, Br?, I?, was also synthesized. The solution chemistry of these complexes was explored through detailed solution‐phase electrochemistry and 1H NMR experiments and showed a unique shift in the ratio of species with inner‐ and outer‐sphere anions with size of the anionic X? group. DFT calculations on the series of calculations corroborated the experimental findings. 相似文献
11.
Marboutin L Petitjean H Xerri B Vita N Dupeyrat F Flament JP Berthomieu D Berthomieu C 《Angewandte Chemie (International ed. in English)》2011,50(35):8062-8066
Vibrations of the metal active site of the Cu,Zn-superoxide dismutase enzyme were analyzed by far-infrared difference spectroscopy and theoretical normal mode calculation. Both electrochemically triggered Cu(I) and Cu(II) redox states show well-defined infrared vibrational modes, notably modes of the histidine ligands, the Cu(II) -His(61) -Zn(II) bridge and of the water pseudo-ligand. 相似文献
12.
Reyes Malavé Osuna Víctor Hernández Prof. Dr. Juan T. López Navarrete Prof. Dr. Juan Aragó Pedro M. Viruela Prof. Dr. Enrique Ortí Prof. Dr. Yoshitake Suzuki Prof. Dr. Shigehiro Yamaguchi Prof. Dr. John T. Henssler Prof. Dr. Adam J. Matzger Prof. Dr. 《Chemphyschem》2009,10(17):3069-3076
Herein, we study the π‐conjugational properties of a homologous series of all‐anti oligothienoacenes containing four to eight fused thiophene rings by means of FT Raman spectroscopy and DFT calculations. The theoretical analysis of the spectroscopic data provides evidence that selective enhancement of a very limited number of Raman scatterings is related to the occurrence in these oligothienoacenes of strong vibronic coupling between collective ν(C?C) stretching modes in the 1600–1300 cm?1 region and the HOMO/LUMO frontier orbitals (HOMO=highest occupied molecular orbital; LUMO=lowest unoccupied molecular orbital). The correlation of the Raman spectroscopic data and theoretical results for these all‐anti oligothienoacenes with those previously collected for a number of all‐syn oligothienohelicenes gives further support to the expectation that cross‐conjugation is dominant in heterohelicenes. Fully planar all‐anti oligothienoacenes display linear π conjugation which seemingly does not reach saturation with increasing number of annulated thiophene rings in the oligomeric chain at least up to the octamer. 相似文献
13.
Maron L Dommergue A Ferrari C Delacour-Larose M Faïn X 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(27):8322-8329
Reactions of elementary mercury in the gas phase (GEM) have been investigated at the DFT level in the presence of halogen radicals and/or halogen anions. In the presence of radicals, the formation of HgX(3)* and HgX(4)* is predicted to be favourable. Moreover, in the presence of anions, the free-radical liberation is enhanced from these two species allowing the presence of halogen free radicals even without the presence of light radiation. This enhancement is associated with the formation of HgX(3)(-), which is predicted to be the most stable species. In solution, redox chemistry can occur and transform GEM in the presence of X(2). The redox potentials of the couples HgX(2)/Hg for X=Cl, Br and I were calculated to be 0.52, 0.48 and 0.04 V, respectively. This study gives new opportunities to elucidate the environmental chemistry of Hg in the polar regions. In these areas GEM has a unique and fast reactivity due to a combination of factors such as the polar sunrise, the presence of halogenated radicals, snow and ice surfaces and cold temperatures. This reactivity, known as atmospheric mercury depletion events (AMDEs), leads to the deposition of significant amounts of Hg(2+) in these regions. The reaction pathways of AMDEs are as yet unknown and the DFT approach may contribute to their elucidation and to the proposal of new mechanisms. Additionally, this study introduces hypotheses concerning the reactivity of GEM inside snowpacks. 相似文献
14.
Water Adsorption and Dissociation on Ceria‐Supported Single‐Atom Catalysts: A First‐Principles DFT+U Investigation
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Zhong‐Kang Han Prof. Dr. Yi Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2092-2099
Single‐atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on‐site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO2(111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO2(111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO2(111) surface and dissociative adsorption on STMA/CeO2(111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized Brønsted–Evans–Polanyi principle. By combining the oxygen spillovers, single‐atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria‐supported single‐atom catalysts for reactions in which the dissociation of water plays an important role, such as the water–gas shift reaction. 相似文献
15.
António J. M. Ribeiro Dr. Marta E. Alberto Prof. Maria J. Ramos Prof. Pedro A. Fernandes Prof. Nino Russo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14081-14089
In order to elucidate the catalytic mechanism of the Mn–Mn containing serine/threonine protein phosphatase 5 (PP5), we present a density functional theory study with a cluster model approach. According to our results, the reaction occurs through an in‐line concerted transition state with an energy of 15.8 kcal mol?1, and no intermediates are formed. The important role played by His304 and Asp274 as stabilizers of the leaving group has been shown, whereas the role played by the metal ions seems to be mostly electrostatic. The indispensable requirement of having a neutral active center has been demonstrated by testing different protonation states of the cluster model. We have shown also the importance of describing properly the electronic configuration of the Mn–Mn binuclear centers. 相似文献
16.
Mechanism of Redox‐Active Ligand‐Assisted Nitrene‐Group Transfer in a ZrIV Complex: Direct Ligand‐to‐Ligand Charge Transfer Preferred
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Dr. Soumya Ghosh Prof. Dr. Mu‐Hyun Baik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1780-1789
The mechanism of the nitrene‐group transfer reaction from an organic azide to isonitrile catalyzed by a ZrIV d0 complex carrying a redox‐active ligand was studied by using quantum chemical molecular‐modeling methods. The key step of the reaction involves the two‐electron reduction of the azide moiety to release dinitrogen and provide the nitrene fragment, which is subsequently transferred to the isonitrile substrate. The reducing equivalents are supplied by the redox‐active bis(2‐iso‐propylamido‐4‐methoxyphenyl)‐amide ligand. The main focus of this work is on the mechanism of this redox reaction, in particular, two plausible mechanistic scenarios are considered: 1) the metal center may actively participate in the electron‐transfer process by first recruiting the electrons from the redox‐active ligand and becoming formally reduced in the process, followed by a classical metal‐based reduction of the azide reactant. 2) Alternatively, a non‐classical, direct ligand‐to‐ligand charge‐transfer process can be envisioned, in which no appreciable amount of electron density is accumulated at the metal center during the course of the reaction. Our calculations indicate that the non‐classical ligand‐to‐ligand charge‐transfer mechanism is much more favorable energetically. Utilizing a series of carefully constructed putative intermediates, both mechanistic scenarios were compared and contrasted to rationalize the preference for ligand‐to‐ligand charge‐transfer mechanism. 相似文献
17.
18.
Daniel Lupp Dr. Niels Johan Christensen Dr. Johannes R. Dethlefsen Dr. Peter Fristrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3435-3442
The mechanism of the molybdenum‐catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an MoVI oxo complex, oxidative cleavage of the diol resulting in an MoIV complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum‐catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum‐catalyzed biomass transformations. 相似文献
19.
Dr. Francisco Núñez‐Zarur Dr. Xavier Solans‐Monfort Prof. Roser Pleixats Dr. Luis Rodríguez‐Santiago Prof. Mariona Sodupe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14553-14565
DFT (B3LYP‐D) calculations have been used to better understand the origin of the recovered Hoveyda–Grubbs derivative catalysts after ring‐closing diene or enyne metathesis reactions. For that, we have considered the activation process of five different Hoveyda–Grubbs precursors in the reaction with models of usual diene and enyne reactants as well as the potential precursor regeneration through the release/return mechanism. The results show that, regardless of the nature of the initial precursor, the activation process needs to overcome relatively high energy barriers, which is in agreement with a relatively slow process. The precursor regeneration process is in all cases exergonic and it presents low energy barriers, particularly when compared to those of the activation process. This indicates that the precursor regeneration should always be feasible, unlike the moderate recoveries sometimes observed experimentally, which suggests that other competitive processes that hinder recovery should take place. Indeed, calculations presented in this work show that the reactions between the more abundant olefinic products and the active carbenes usually require lower energy barriers than those that regenerate the initial precatalyst, which could prevent precursor regeneration. On the other hand, varying the precursor concentration with time obtained from the computed energy barriers shows that, under the reaction conditions, the precursor activation is incomplete, thereby suggesting that the origin of the recovered catalyst probably arises from incomplete precursor activation. 相似文献
20.
C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands
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Jérémy Jacquet Pauline Chaumont Geoffrey Gontard Dr. Maylis Orio Dr. Hervé Vezin Dr. Sébastien Blanchard Dr. Marine Desage‐El Murr Prof. Louis Fensterbank 《Angewandte Chemie (International ed. in English)》2016,55(36):10712-10716
The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low‐valent counterpart bearing reduced ligands, this complex performs high‐yielding C?N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high‐valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high‐valent metallic species. 相似文献