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Synthesis and structural characterization of the first bis(benzimidazolin- 2-ylidene) complexes of nickel(II)

The reaction of Ni(OAc)2 with the benzimidazolium salts 1,3-dimethylbenzimidazolium iodide (1), 1,3-bis(2-propenyl)benzimidazolium bromide (2), 1,3-dipropylbenzimidazolium bromide (3), 1-(2-propenyl)-3- methylbenzimidazolium bromide (6), and 1-propyl-3-methylbenzimidazolium iodide (7) in molten [Bu4N]X (X = Br, I, BF4) as ionic liquid afforded novel square-planar nickel(II) bis(benzimidazolin-2-ylidene) complexes of the general formula trans-[NiX2(NHC)2] (X = I, NHC = 1,3-dimethylbenzimidazolin-2-ylidene, 8; X = Br, NHC = 1,3-bis(2-propenyl) benzimidazolin-2-ylidene, 9; X = Br, NHC = 1,3-dipropylbenzimidazolin-2-ylidene, 10; X = Br, NHC = 1-(2-propenyl)-3-methylbenzimidazolin-2-ylidene, 11; X = I, NHC = 1-propyl-3-methylbenzimidazolin-2-ylidene, 12). X-ray diffraction studies of 8-12 reveal a square-planar coordination geometry for all complexes with the carbene ligands arranged in a trans fashion.

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NHC-Palladium(II) Mononuclear and Binuclear Complexes Containing Phenylene-Bridged Bis(thione) Ligands: Synthesis, Characterization, and Catalytic Activities

A series of mono- and binuclear Pd(II) complexes with N-heterocyclic carbene (NHC) and phenylene-bridged bis(thione) (SCS) ligands were prepared and characterized by 1H and 13C NMR spectroscopy, IR, and mass spectrometry. The molecular structures of 1b, 2a, and 3b have been determined by the single-crystal X-ray diffraction method. The catalytic activities of the synthesized palladium complexes in the regioselective reduction of quinolines to the corresponding 1,2,3,4-tetrahydroquinolines were thoroughly investigated with ammonia-borane under mild reaction conditions. It is observed that the activities of the binuclear Pd(NHC) complexes were higher than those of the corresponding mononuclear complexes under the same conditions.

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Dual functional hetero-anthracene based single component organic ionic conductors as redox mediator cum light harvester for solid state photoelectrochemical cells

We have synthesized a novel solid organic ionic conductor (SOIC) that acts as a redox mediator and a light absorbing material at the same time. Such dual function of SOICs has not been reported before. It was achieved by substituting N,N?-dimethyl benzimidazolium iodide (BIMI) with hetero-anthracene (phenoxazine (POZ)/phenothiazine (PTZ)) which are labeled as SOIC-1 and SOIC-2, respectively. These substitutions caused the absorption spectrum of BIMI to be extended over 100 nm into the red spectrum and at the same time exhibit excellent redox capability and ionic conductivity. In addition, these synthesized SOICs also enhance the total electron injection into the TiO2 matrix with the metal-free SK3 dye sensitizer. Density functional theory (DFT) was used to optimize the structure and geometrical arrangement of the SOICs. To evaluate the role of PTZ/POZ substitution on BIMI and how pore filling can affect the device performance, solid-state DSSC (ss-DSSC) devices were prepared with two different thickness of TiO2 (8 mum and 12 mum) photoanode. The 8 mum thick TiO2 photoanode with SOIC-1 has an overall PCE of 7.9% which is about 72% higher than the unmodified BIMI (PCE of 4.4%) under AM1.5 illumination. Last but not least, the synthesized SOICs have high thermal stability up to 120 C which is way beyond the operating temperatures of solar cells which make them ideal for real-world applications.

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Deactivation of a ruthenium(II) N-heterocyclic carbene p-cymene complex during transfer hydrogenation catalysis

A ruthenium (II) N-heterocyclic carbene (NHC) complex was synthesized to investigate ligand dissociation as a possible deactivation pathway for the catalytic cycle of a transfer hydrogenation reaction. Diiodo(1,3-dimethylbenzimidazole-2-ylidene)(p-cymene)ruthenium(II) was synthesized for use as the catalytic species and characterized using physico-chemical, spectroscopic methods, and single crystal X-ray diffraction. The transfer of hydrogen from isopropanol to acetophenone was followed using 1H NMR. We observed 94% conversion of the substrate to the alcohol product after 1?h. We also found that the p-cymene complex decomposed during the catalytic reaction to the extent of 80% deactivation after 1?h, based on 1H NMR spectrometry. From Gaussian calculations, an ultraviolet?visible spectrum that is in excellent agreement with the actual spectrum was computed, giving insight into the nature of the absorptions observed experimentally.

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Evaluation of arene ruthenium(ii) N-heterocyclic carbene complexes as organometallics interacting with thiol and selenol containing biomolecules

Metal complexes with N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry and are now increasingly considered for the development of new chemical tools and metal based drugs. Ruthenium complexes of the type (p-cymene)(NHC)RuCl2 interacted with biologically relevant thiols and selenols, which resulted in the inhibition of enzymes such as thioredoxin reductase or cathepsin B. Pronounced antiproliferative effects could be obtained provided that an appropriate cellular uptake was achieved. Inhibition of tumor cell growth was accompanied by a perturbation of metabolic parameters such as cellular respiration. The Royal Society of Chemistry 2013.

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Azolium salts as effective catalysts for benzoin condensation and related reactions

A catalytic ability of several azolium salts for benzoin condensation, the benzoylation of 4-chloro-1-phenyl-1H-pyrazolo[3,4-d]pyrimidine, and oxidative aroylation was examined. We found that azolium salts having an imidazolium moiety, such as 1,4-dimethyl-1,2,4-triazolium iodide (3), and 2-methylpyrido[1,2-c]- (4), dipyrido[1,2-c:2?,1?-e]- (5), naphtho[1,2-c]- (10), and phenanthro[9,10-c]imidazolium iodide (11) can be used as effective catalysts for benzoin condensation and related reactions.

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Reactivity of Tetracyanoethylene Oxide toward Heteroaromatic Compounds. Synthesis and Structure of Heterocyclic Dicyanomethylides

Tetracyanoethylene oxide (TCNEO) was allowed to react with 17 heterocyclic derivatives, mainly azoles.Only in ten cases the reaction affords the corresponding dicyanomethylide.The structure of these compounds was established by IR and 1H NMR spectroscopies.The reactivity of heterocycles toward TCNEO increases with basicity and decreases with steric hindrance.A bidimensional plot of our results and those of the literature shows a clear frontier between reactive and unreactive heterocycles.

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Palladium catalyst coordinated in knitting N-heterocyclic carbene porous polymers for efficient Suzuki-Miyaura coupling reactions

Three N-heterocyclic carbenes (NHCs) were successfully integrated into the skeleton of hyper-crosslinked polymers (HCPs) via an external cross-linking reaction. The structure and composition of the solid catalyst was characterized by SEM, N2 sorption, FT-IR, XPS and CP/MAS NMR. Depending on the nature of the NHCs, the Brunauer-Emmett-Teller (BET) surface area of HCPs could be tuned and a BET surface area as high as 1229 m2 g-1 was achieved. The Poly-NHC-2-Pd2+ catalyst afforded rapid conversion for the Suzuki-Miyaura cross-coupling reactions of various aryl halides and arylboronic acids even at a Pd loading of 0.057 mmol% in aqueous media. In particular, because of the substantial porosity and individual pore structure toward the entrapped Pd species, Poly-NHC-2-Pd2+ showed outstanding stability and recyclability, which could be reused at least 5 times without significant loss of activity. The developed microporous catalyst combined with the NHC-functionalize is one of the most efficient heterogeneous systems for Suzuki-Miyaura cross-coupling reactions of aryl halides.

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Controlling the solid-state luminescence of gold(I) N-heterocyclic carbene complexes through changes in the structure of molecular aggregates

Thermally stable, solid-state luminescent organic materials are highly desired for the development of practical applications. Herein we synthesized new gold(I) complexes with N-heterocyclic carbene ligands, which have the ability to form strong metal-organic bond. Consequently, their thermochemical stability is enhanced at temperatures around 300 C. Precise design of the molecular structure of the ligands, with a focus on ensuring low steric hindrance around Au atoms in order to limit disturbances to Au/Au interactions, provided a complex with a densely packed crystal with a shorter intermolecular Au?Au distance (3.17 A) than the typical distance. In the solid state, this complex exhibited strong aurophilic interactions, which generated intense phosphorescence even in air at room temperature (quantum yield=16%) in spite of absence of any phosphorescence in solution. This behavior is characteristic for solid-state luminescence referred to as aggregation-controlled emission. Furthermore, the gold (I) complex displays capacity for mechano- and vapo-chromism?that is, the ability to change color reversibly in response to the application of external stimuli. We believe that the proposed design framework, which involves controlling thermal stability and luminescence property separately, provides a new opportunity for the development of practical applications using solid-state luminescent organic molecules.

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[NiX2(NHC)2]complexes in the hydrosilylation of internal alkynes

A number of nickel(II) dihalide complexes with small monodentate N-heterocyclic carbene ligands was synthesized and tested for their catalytic activity in the hydrosilylation of internal alkynes. The nickel(0) active species was obtained from the starting nickel(II) complex by reduction with diethylzinc. In all cases the catalytic reaction yielded the syn product selectively. The fastest catalysts reached full conversion of the symmetric alkyne 3-hexyne in 60 min at 50 C, with 5 mol-% catalyst loading. The asymmetrically substituted internal alkyne 1-phenyl-1-propyne gave full conversion within 30 min. The major product (83%) was shown to be the expected (E)-1-phenyl-1-(triethylsilyl)propene. The active catalyst was demonstrated to be a homogeneous species. Nickel(II) complexes bearing monodentate N-heterocyclic carbene ligands with small N-substituents were prepared and tested in the catalytic hydrosilylation of internal alkynes. The complexes are active catalysts after treatment with diethylzinc. The catalytically active compound is shown to be a homogeneous species.

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