- Cu-catalyzed controllable C-H mono-/di-/triarylations of imidazolium salts for ionic functional materials
-
Herein the Cu-catalyzed direct C-H mono-, di- and triarylations of imidazolium salts with aryl iodides/bromides are accomplished for the first time. The unprecedented alkenylation and alkynylation are also realized using alkenyl and alkynyl iodides, respectively. Moreover, triarylated imidazolium salts with different substituents can be accessed in a modular and one-pot manner. This protocol provides an efficient tool for the assembly of diverse imidazolium-based ionic functional materials. As applicable examples, an electrochromic bisbenzimidazolium salt 7 and a photochromic triarylimidazolium salt 8 are easily obtained.
- Li, Shiqing,Tang, Junbin,Zhao, Yinsong,Jiang, Ruyong,Wang, Tianbao,Gao, Ge,You, Jingsong
-
-
Read Online
- Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes
-
Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is
- Iakovenko, Roman,Hlavá?, Jan
-
supporting information
p. 440 - 446
(2021/01/28)
-
- Host–Guest Interactions in a Metal–Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction
-
A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3(4,4′-dcbpy)] and a photosensitizer [Ru(bpy)2(5,5′-dcbpy)]Cl2 using the isoreticular series of metal–organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location—either at the outer MOF particle surface or inside the MOF cavities—affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.
- Casini, Angela,Fischer, Roland A.,Haimerl, Johanna,Rieger, Bernhard,Schuster, Michael,Shustova, Natalia B.,Stanley, Philip M.,Thomas, Christopher,Urstoeger, Alexander,Warnan, Julien
-
p. 17854 - 17860
(2021/06/11)
-
- Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO2 to Formate by Ruthenium Complexes
-
A series of 4,4′-dimethyl-2,2′-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO2 to formate in acetonitrile (CH3CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO2 from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO2 from CH3CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO2 to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.
- Sampaio, Renato N.,Grills, David C.,Polyansky, Dmitry E.,Szalda, David J.,Fujita, Etsuko
-
p. 2413 - 2428
(2020/02/13)
-
- Addressing Reversibility of R-NHC Coupling on Palladium: Is Nano-to-Molecular Transition Possible for the Pd/NHC System?
-
It has recently been shown that palladium-catalyzed reactions with N-heterocyclic carbene (NHC) ligands involve R-NHC coupling accompanied by transformation of the molecular catalytic system into the nanoscale catalytic system. An important question appeared in this regard is whether such a change in the catalytic system is irreversible. More specifically, is the reverse nano-to-molecular transformation possible? In view of the paramount significance of this question to the area of catalyst design, we studied the capability of 2-substituted azolium salts to undergo the breakage of C-C bond and exchange substituents on the carbene carbon with corresponding aryl halides in the presence of Pd nanoparticles. The study provides important experimental evidence of possibility of the reversible R-NHC coupling. The observed behavior indicates that the nanosized metal species are capable of reverse transition to molecular species. Such an option, known for phosphine ligands, was previously unexplored for NHC ligands. The present study for the first time demonstrates bidirectional dynamic transitions between the molecular and nanostructured states in Pd/NHC systems. As a unique feature, surprisingly small activation barriers (18 kcal/mol) and noticeable thermodynamic driving force (-5 to -7 kcal/mol) were calculated for C-C bond oxidative addition to Pd(0) centers in the studied system. The first example of NHC-mediated Pd leaching from metal nanoparticles to solution was observed and formation of Pd/NHC complex in solution was detected by ESI-MS.
- Denisova, Ekaterina A.,Eremin, Dmitry B.,Gordeev, Evgeniy G.,Tsedilin, Andrey M.,Ananikov, Valentine P.
-
p. 12218 - 12227
(2019/09/30)
-
- An unexpected iron (II)-based homogeneous catalytic system for highly efficient CO2-to-CO conversion under visible-light irradiation
-
We present two as-synthesized Fe(II)-based molecular catalysts with 1,10-phenanthroline (phen) ligands; Fe(phen)3Cl2 (1) and [Fe(phen)2(CH3CH2OH)Cl]Cl (2), and their robust catalytic properties for the conversion of CO2 to CO in DMF/TEOA (DMF = N,N’-dimethylformamide; TEOA = triethanolamine) solution containing Ru(bpy)32+ and BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo-[d]-imidazole). High turnover numbers (TONs) of 19,376 were achieved with turnover frequencies (TOFs) of 3.07 s?1 for complex 1 (1.5 × 10?7 M). A quantum efficiency of 0.38% was observed after 5 h irradiated by 450 nm monochromatic light. The generation rate of CO2 and H2 were tuned by optimizing the experimental conditions, resulting in a high CO selectivity of 90%. The remarkable contribution of the photosensitizer to the total TONCO was found being 19.2% (as shown by tests under similar conditions without catalysts) when BIH was employed as a sacrificial electron donor. The product selectivity in complex 2 reached 95%, and the corresponding TONCO and TOFCO were 33,167 and 4.61 s?1 in the same concentration with complex 1 used as catalyst; respectively. This work provides guidance for future designs of simple, highly efficient and selective molecular catalytic systems that facilitate carbon-neutral solar-to-fuel conversion processes
- Fu, Zi-Cheng,Mi, Cheng,Sun, Yan,Yang, Zhi,Xu, Quan-Qing,Fu, Wen-Fu
-
-
- Microwave assisted synthesis and potent antimicrobial activity of some novel 1,3-dialkyl-2-arylbenzimidazolium salts
-
Background: Benzimidazolium salts include biologically active benzimidazole ring. Some benzimidazolium salts and their metal complexes, containing different groups, showed remarkable antibacterial, antifungal and antitumor effects. Most of these studies are generally related with the 2-unsubstituted derivatives of benzimidazolium salts which named as N-heterocyclic carbenes (NHCs). To enhance the efficacy of the benzimidazoles in the biological systems, it is very important to overcome the insolubility problem. For this reason and previously indicated structural importance of the benzimidazolium salts, 1,3-dialkyl halide salts of the 2-arylbenzimidazoles, are of focus in this work. To the best of our knowledge, this is the first report that describes the microwave assisted synthesis and antimicrobial activity of 2-arylsubstituted benzimidazolium salts. Methods: A series of novel 1,3-dialkyl-2-arylbenzimidazolium salts (8-28) were synthesized via the N-alkylation of 1-methyl-2-arylbenzimidazole derivatives (1-7) with alkyl halides under microwave conditions by using small amount of DMF. The results were also compared with conventional heating under reflux. Structures of the products were confirmed by using 1H-NMR, 13C-NMR, FTIR spectroscopic techniques. All of the synthesized compounds were screened for their in vitro antimicrobial activities using microbroth tube dilution and disc diffusion methods. Results: Considering the reactions repeated by classical heating, it was determined that the reaction times were decreased from 3-6 hours to 5-35 minutes under microwave. Additionally, yields have increased from 4-71 % to 64-96 % ranges. Considering the whole antimicrobial activity studies, MIC values of newly synthesized benzimidazolium salts 8-28 (1.95->1500 μg/ml) are remarkably smaller than parent benzimidazoles 1-7 (62.5->1500 μg/ml) on the studied microorganisms. Conclusion: The microwave method is advantageous regarding the usage of mild conditions and small amounts of solvent, easy purification and achieving high yields in short times. The antimicrobial activity studies demonstrate that newly synthesized salts (8-28) are effective mostly on grampositives and eukaryotic microorganisms. Compounds 16, 18, 19, 24, 25 and 27 were found to be the most effective inhibitors of growth in both gram-positive bacteria and eukaryotes. Thus, the synthesized compounds in this study may aid the treatment of fungal and bacterial diseases. The results of this study are of great significance in the areas of synthetic organic chemistry, microbiology, pharmaceutical chemistry and chemical catalysis.
- Eren, Bilge,Yilmaz, ?zge,?etin, Gül?in,Darcan, Cihan
-
p. 621 - 633
(2018/06/06)
-
- A New Mode of Operation of Pd-NHC Systems Studied in a Catalytic Mizoroki-Heck Reaction
-
Metal complexes bearing N-heterocyclic carbene (NHC) ligands are typically considered the system of choice for homogeneous catalysis with well-defined molecular active species due to their stable metal-ligand framework. A detailed study involving 19 different Pd-NHC complexes with imidazolium, benzimidazolium, and triazolium ligands has been carried out in the present work and revealed a new mode of operation of metal-NHC systems. The catalytic activity of the studied Pd-NHC systems is predominantly determined by the cleavage of the metal-NHC bond, while the catalyst performance is strongly affected by the stabilization of in situ formed metal clusters. In the present study, the formation of Pd nanoparticles was observed from a broad range of metal complexes with NHC ligands under standard Mizoroki-Heck reaction conditions. A mechanistic analysis revealed two different pathways to connect Pd-NHC complexes to "cocktail"-type catalysis: (i) reductive elimination from a Pd(II) intermediate and the release of NHC-containing byproducts and (ii) dissociation of NHC ligands from Pd intermediates. Metal-NHC systems are ubiquitously applied in modern organic synthesis and catalysis, while the new mode of operation revealed in the present study guides catalyst design and opens a variety of novel opportunities. As shown by experimental studies and theoretical calculations, metal clusters and nanoparticles can be readily formed from M-NHC complexes after formation of new M-C or M-H bonds followed by C-NHC or H-NHC coupling. Thus, a combination of a classical molecular mode of operation and a novel cocktail-type mode of operation, described in the present study, may be anticipated as an intrinsic feature of M-NHC catalytic systems.
- Astakhov, Alexander V.,Khazipov, Oleg V.,Chernenko, Andrey Yu.,Pasyukov, Dmitry V.,Kashin, Alexey S.,Gordeev, Evgeniy G.,Khrustalev, Victor N.,Chernyshev, Victor M.,Ananikov, Valentine P.
-
p. 1981 - 1992
(2017/06/14)
-
- POLY(PHENYLENE) AND M-TERPHENYL AS PROTECTING GROUPS FOR BENZIMIDAZOLIUM HYDROXIDES
-
The present disclosure provides alkaline-stable m-terphenyl benzimidazolium hydroxide compounds, in which the C2-position is attached to a phenyl group having various substituents at the ortho positions. Polymers incorporating m-terphenylene repeating groups derived from these alkaline-stable benzimidazolium hydroxide compounds are also presented, along with their inclusion in ionic membranes and in electrochemical devices.
- -
-
Page/Page column 40; 41
(2017/08/01)
-
- Visible-Light-Driven Photocatalytic CO2 Reduction by a Ni(II) Complex Bearing a Bioinspired Tetradentate Ligand for Selective CO Production
-
A Ni(II) complex bearing an S2N2-type tetradentate ligand inspired by the active site of carbon monoxide dehydrogenase was found to selectively catalyze CO2 reduction to produce CO in a photocatalytic system using [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) as a photosensitizer and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. The Ni(II) complex shows a high turnover number over 700 with high CO selectivity of >99% and quantum yield of 1.42% in the photocatalytic system.
- Hong, Dachao,Tsukakoshi, Yuto,Kotani, Hiroaki,Ishizuka, Tomoya,Kojima, Takahiko
-
supporting information
p. 6538 - 6541
(2017/06/05)
-
- Earth-abundant photocatalytic systems for the visible-light-driven reduction of CO2 to CO
-
Herein, we report a highly selective photocatalytic system, based on an in situ copper photosensitizer and an iron catalyst, for the reduction of CO2 to CO. Turnover numbers (TON) up to 487 (5 h) with selectivities up to 99% and ΦCO = 13.3% were observed. Stern-Volmer analysis allowed us to establish a reductive quenching mechanism between the Cu PS and electron donor.
- Rosas-Hernández, Alonso,Steinlechner, Christoph,Junge, Henrik,Beller, Matthias
-
supporting information
p. 2356 - 2360
(2017/07/24)
-
- Poly(phenylene) and m-Terphenyl as Powerful Protecting Groups for the Preparation of Stable Organic Hydroxides
-
Four benzimidazolium hydroxide compounds, in which the C2-position is attached to a phenyl group possessing hydrogen, bromine, methyl groups, or phenyl groups at the ortho positions, are prepared and investigated for stability in a quantitative alkaline stability test. The differences between the stability of the various protecting groups in caustic solutions are rationalized on the basis of their crystal structures and DFT calculations. The highest stability was observed for the m-terphenyl-protected benzimidazolium, showing a half-life in 3 m NaOD/CD3OD/D2O at 80 °C of 3240 h. A high-molecular-weight polymer analogue of this model compound is prepared that exhibits excellent mechanical properties, high ionic conductivity and ion-exchange capacity, as well as remarkable hydroxide stability in alkaline solutions: only 5 % degradation after 168 h in 2 m KOH at 80 °C. This is the most stable hydroxide-conducting benzimidazolium polymer to date.
- Wright, Andrew G.,Weissbach, Thomas,Holdcroft, Steven
-
supporting information
p. 4818 - 4821
(2016/04/19)
-
- Photocatalytic Reduction of CO2 with Re-Pyridyl-NHCs
-
A series of Re(I) pyridyl N-heterocyclic carbene (NHC) complexes have been synthesized and examined in the photocatalytic reduction of CO2 using a simulated solar spectrum. The catalysts were characterized through NMR, UV-vis, cyclic voltammetry under nitrogen, and cyclic voltammetry under carbon dioxide. The complexes were compared directly with a known benchmark catalyst, Re(bpy) (CO)3Br. An electron-deficient NHC substituent (PhCF3) was found to promote catalytic activity when compared with electron-neutral and -rich substituents. Re(PyNHC-PhCF3) (CO)3Br was found to exceed the CO production of the benchmark Re(bpy) (CO)3Br catalyst (51 vs 33 TON) in the presence of electron donor BIH and photosensitizer fac-Ir(ppy)3. Importantly, Re(PyNHC-PhCF3) (CO)3Br was found to function without a photosensitizer (32 TON) at substantially higher turnovers than the benchmark catalyst Re(bpy) (CO)3Br (14 TON) under a solar simulated spectrum.
- Huckaba, Aron J.,Sharpe, Emily Anne,Delcamp, Jared H.
-
p. 682 - 690
(2016/01/30)
-
- Highly Robust Hybrid Photocatalyst for Carbon Dioxide Reduction: Tuning and Optimization of Catalytic Activities of Dye/TiO2/Re(I) Organic-Inorganic Ternary Systems
-
Herein we report a detailed investigation of a highly robust hybrid system (sensitizer/TiO2/catalyst) for the visible-light reduction of CO2 to CO; the system comprises 5′-(4-[bis(4-methoxymethylphenyl)amino]phenyl-2,2′-dithiophen-5-yl)cyanoacrylic acid as the sensitizer and (4,4′-bis(methylphosphonic acid)-2,2′-bipyridine)ReI(CO)3Cl as the catalyst, both of which have been anchored on three different types of TiO2 particles (s-TiO2, h-TiO2, d-TiO2). It was found that remarkable enhancements in the CO2 conversion activity of the hybrid photocatalytic system can be achieved by addition of water or such other additives as Li+, Na+, and TEOA. The photocatalytic CO2 reduction efficiency was enhanced by approximately 300% upon addition of 3% (v/v) H2O, giving a turnover number of ≥570 for 30 h. A series of Mott-Schottky (MS) analyses on nanoparticle TiO2 films demonstrated that the flat-band potential (Vfb) of TiO2 in dry DMF is substantially negative but positively shifts to considerable degrees in the presence of water or Li+, indicating that the enhancement effects of the additives on the catalytic activity should mainly arise from optimal alignment of the TiO2 Vfb with respect to the excited-state oxidation potential of the sensitizer and the reduction potential of the catalyst in our ternary system. The present results confirm that the TiO2 semiconductor in our heterogeneous hybrid system is an essential component that can effectively work as an electron reservoir and as an electron transporting mediator to play essential roles in the persistent photocatalysis activity of the hybrid system in the selective reduction of CO2 to CO.
- Won, Dong-Il,Lee, Jong-Su,Ji, Jung-Min,Jung, Won-Jo,Son, Ho-Jin,Pac, Chyongjin,Kang, Sang Ook
-
p. 13679 - 13690
(2015/11/10)
-
- NMR studies of 2-aryl derivatives of benzimidazole, benzimidazolium ion, and benzimidazoline
-
A series of 2-arylbenzimidazoles, 2-aryl-1,3-dimethylbenzimidazolium iodides, and 2-aryl-1,3-dimethylbenzimidazolines were prepared and their NMR spectra were examined. The substituent parameters were calculated for 2-benzimidazolyl, 2-benzimidazoliumyl, and 2-benzimidazolinyl groups on the chemical shifts of the protons and the carbons of benzene ring. The 2-benzimidazoliumyl group was found to cause a significant up-field shift of the ipso-carbon signal and down-field shift for the ortho- and para-carbon signals. On the other hand, the 2-benzimidazolyl and the 2-benzimidazolinyl groups cause down-field shift of the ipso-carbon signals but cause almost negligible change on the other carbon signals.
- Lee, Chang Kiu,Lee, In-Sook Han
-
experimental part
p. 425 - 433
(2009/06/18)
-
- Marcus theory of a parallel effect on α for hydride transfer reaction between NAD+ analogues
-
Rate and equilibrium constants for hydride transfer from a series of 1,3-dimethyl-2-substituted phenylbenzimidazolines to a pyridinium ion, a quinolinium ion, and a phenanthridinium ion have been evaluated. Each oxidizing agent gives a linear Bronsted plot with slope, α. The α values vary systematically with the spontaniety of the reactions. They are in reasonable agreement with the predictions of modified Marcus theory. Their trend is very accurately predicted, showing a parallel (Leffler-Hammond) effect. These results make a multistep mechanism, involving high energy intermediates, very unlikely.
- Lee, In-Sook Han,Jeoung, Eun Hee,Kreevoy, Maurice M.
-
p. 2722 - 2728
(2007/10/03)
-
- Investigations of unsaturated azoles. 13. Synthesis and some reactions of 1-alkylbenzimidazoles
-
Methods of direct alkylation of benzimidazoles by haloalkanes in homogeneous medium and under phase transfer catalysis conditions together with cyanoethylation by acrylonitrile are reported. The dealkylation of quaternary benzimidazole salts was also studied. 1997 Plenum Publishing Corporation.
- Popov
-
p. 672 - 681
(2007/10/03)
-