Synthesis and structural characterization of novel bridged platinum(II) biscarbene complexes

Novel bridged platinum(II) biscarbene complexes are reported: 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) (3) and 1,1′-dimethyl-3,3′-ethylene-4-diimidazolin-2,2′-diylidene platinum(II) complexes 4 are directly accessible in high yields starting from platinum halides. The one-pot synthesis obviates the need for multi-step reactions via metal precursors or free carbenes. An X-ray crystal structure of 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) dibromide (3b) confirmed the structural similarity to the known corresponding palladium complexes. Since free 1,1′-di-R-3,3′-methylene-4-diimidazolin-2,2′-diylidenes are only available in low yields this synthetic route provides an easy access to the corresponding carbene complexes.     

Amphiphilic polymer supported N-heterocyclic carbene palladium complex for Suzuki cross-coupling reaction in water

We synthesized amphiphilic polymer-supported N-heterocyclic carbene (NHC) precursor resins by loading polyethylene glycol (PEG) containing imidazolium groups on Merrifield resin. These PS-PEG-NHC precursor resins were compatible with water and readily formed a stable complex with palladium. These PS-PEG-NHC-Pd catalysts showed excellent catalytic activity for Suzuki cross-coupling reactions of various aryl iodides and bromides with phenylboronic acid in water than the previously described polystyrene based catalysts. In addition, the PS-PEG-NHC-Pd catalysts continued to provide excellent catalytic activity in Suzuki cross-coupling reactions after five consecutive recycles.     

N-Heterocyclic carbene-palladium complex on polystyrene resin surface as polymer-supported catalyst and its application in Suzuki cross-coupling reaction

A poly(imidazoliummethyl styrene)-surface grafted-polystyrene resin was prepared by suspension polymerization. This was used as the polymer-supported carbene precursor for the palladium complex, which efficiently catalyzed the Suzuki cross-coupling of aryl halides and phenylboronic acid.     

A Series of Iron(II)-NHC Sensitizers with Remarkable Power Conversion Efficiency in Photoelectrochemical Cells**

A series of six new Fe(II)NHC-carboxylic sensitizers with their ancillary ligand decorated with functions of varied electronic properties have been designed with the aim to increase the metal-to- surface charge separation and light harvesting in iron-based dye-sensitized solar cells (DSSCs). ARM130 scored the highest efficiency ever reported for an iron-sensitized solar cell (1.83 %) using Mg²⁺ and NBu₄I-based electrolyte and a thick 20 μm TiO₂ anode. Computational modelling, transient absorption spectroscopy and electrochemical impedance spectroscopy (EIS) revealed that the electronic properties induced by the dimethoxyphenyl-substituted NHC ligand of ARM130 led to the best combination of electron injection yield and spectral sensitivity breadth.     

Synthesis and Structures of Arene Ruthenium (II)–NHC Complexes: Efficient Catalytic α‐alkylation of ketones via Hydrogen Auto Transfer Reaction

A panel of six new arene Ru (II)‐NHC complexes 2a‐f , (NHC = 1,3‐diethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1a , 1,3‐dicyclohexylmethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1b and 1,3‐dibenzyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1c ) were synthesized from the transmetallation reaction of Ag‐NHC with [(η⁶‐arene)RuCl₂]₂ and characterized. The ruthenium (II)‐NHC complexes 2a‐f were developed as effective catalysts for α‐alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5 mol% catalyst load in 8 h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations.     

Ru(II)‐based antineoplastic: A “wingtip” N‐heterocyclic carbene facilitates access to a new class of organometallics that are cytotoxic to common cancer cell lines

The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )₂][PF₆], [Au( 1 )₂][PF₆] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF₆] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent.     

Palladium(II) complexes bearing N‐alkylpiperidoimidazolin‐2‐ylidene derivatives: Effect of alkyl chain length of ligands on catalytic activity

A series of piperidoimidazolinium salts which differ in the chain lengths (butyl, octyl, dodecyl, octadecyl) and their Pd–N‐heterocyclic carbene complexes with pyridine were synthesized and characterized using elemental analysis and spectroscopic methods. The effects of these ligands on catalyst activation and the performance of the complexes were studied in Suzuki–Miyaura reactions of arylboronic acid with aryl chlorides. The complex with the ligand having the longest chain length was found to be most active. The results demonstrated that the length of the alkyl chain of the piperidoimidazolin‐2‐ylidene controlled the dispersion and composition of the nanoparticles and it affected the catalytic activity. The impact of alkyl chain length of piperidoimidazolin‐2‐ylidene on the Suzuki–Miyaura reactions of arylboronic acid with aryl halides was systematically investigated.     

Identification of radical structures on 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5‐dimethylbenzimidazoliumsilver(I)bromide exposed to gamma rays: an EPR study

1‐Pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide and 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide and their Ag⁺ complexes were synthesized and their polycrystal forms were produced by recrystallization in dichloromethane/Et₂O solvent system. Structural determinations were carried out by ¹H NMR and ¹³C NMR with a Varian 400 NMR system using tetramethylsilane as internal standard and CDCl₃ as solvent. The disappearance of acidic N‐heterocyclic carbene proton showed the formation of Ag(I) complexes. Also, elemental analyses were carried out. Electron paramagnetic resonance (EPR) measurements were performed to determine the formed radical structure on the samples irradiated at the room temperature for 72 h by using ⁶⁰Co‐source with dose rate of 0.680 kGy. The EPR measurements were carried out in the temperature range of 200 K–450 K. Identical radicals were determined on the irradiated compounds. It was observed that the shapes of the spectra of the samples were independent of the temperature but, the resonance line intensities changed linearly with the temperature. Also, it was detected that the free radical on the 1‐pentamethylbenzyl‐3‐ethylimidazoliumsilver(I)bromide is not stable compared to that on the 1,3‐bis(pentamethylbenzyl)‐4,5dimethylbenzimidazoliumsilver(I)bromide. Copyright © 2016 John Wiley & Sons, Ltd.     

SiO2-NHC-CuI–Catalyzed N-Arylation of Imidazoles with Arylboronic Acids Under Base-Free Reaction Conditions

N-Arylation of imidazoles with arylboronic acids was efficiently carried out in the presence of a catalytic amount of SiO₂-NHC-Cu^I in methanol at room temperature under base-free reaction conditions. The reactions of a variety of arylboronic acids with imidazoles generated the corresponding products N-arylimidazoles in good to excellent yields. In addition, SiO₂-NHC-Cu^I could be recovered and recycled for six consecutive trials without significant loss of its reactivity.     

Pd–NHC Catalyzed Biaryl Coupling by Direct C–H Activation—A Novel Strategy for the Synthesis of Dibenzocyclooctane Lignans

Cross-coupling reactions, such as Buchwald-Hartwig arylamination and direct intramolecular biaryl coupling by C–H activation, were carried out using various Palladium-N-heterocyclic carbenes (Pd–NHC) as catalysts. The yields were good to excellent. The latter strategy was adopted to transform two dibenzylbutane lignans, isolated from the leaves of Ocotea macrophylla (Lauraceae), into the corresponding dibenzocyclooctane lignans in good overall yields.

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