Asymmetric Hydrosilylation of Aromatic Ketones Catalyzed by an Economical and Effective Copper-Diphosphine Catalytic System in Air

In the presence of the inexpensive and non‐toxic polymethylhydrosiloxane, the combination of copper(II) acetate and a chiral diphosphine displayed high catalytic efficiency in the asymmetric hydrosilylation of a series of aromatic ketones in air atmosphere and at room temperature. (R)‐1‐Arylethanols were obtained with up to 99% yield and 93% enantiomeric excess. Meanwhile, the electron effect and steric hindrance of substituents on the aromatic ring had an interesting influence on both the yields and enantioselectivities. Furthermore, a possible mechanism was presented to explain the influence of some key factors on the reaction.     

Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators

Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt₃, PCy₃, and P(o‐tol)₃ were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy₃ or P(o‐tol)₃ exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt₃ did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)₃ can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463     

Synthesis,Crystal Structure,and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999.     

Cu (II) and Co (II/III) complexes of N,O‐chelated Schiff base ligands: DNA interaction,protein binding,cytotoxicity, cell death mechanism and reactive oxygen species generation studies

A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH ₂ (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH ₂ = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC₅₀ values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished.     

Novel flame retardant paint based on Co(II) and Ni(II) metal complexes as new additives for surface coating applications

The study is focused on the synthesis of a new Co(II) and Ni(II) metal complexes, which is synthesized by the reaction of the isatin 4‐aminoantipyrine Schiff base ligand with selected divalent Co(II) and Ni(II) ions and their possible applications as flame retardant additives in paint formulations for surface coating application. The prepared metal complexes were characterized using a combination of Fourier transform infrared, elemental analysis, proton nuclear magnetic resonance, ¹³C‐NMR spectra, and mass spectroscopy. The prepared Schiff base ligand metal complexes were physically added to alkyd paint formulation to give coating formulations at a laboratory scale and then applied onto plywood and steel panels using a brush. The ignitability and oxygen index values obtained indicated that the paint which contained the prepared Co(II) and Ni(II) metal complexes as additives exhibited very good flame retardant. The physical and mechanical characteristics of the coatings were studied in order to estimate any disadvantages due to the incorporation of the additives. It was discovered that the added substances did not impact the hardness, flexibility, and adhesion of the prepared coating films. The gloss of the paint formulation film was improved due to the incorporation of the aromatic ring into the formulation and the level of the oil percent.     

Enhanced Performance of Organic/Inorganic Hybrid Nanomaterials bearing Impregnated [PdL2] Complexes as Counter‐Electrode Catalyst for Dye‐Sensitized Solar Cells

N‐coordinate Pd²⁺ complexes [PdL₂] (L: N‐N‐quinoline‐8‐yl‐R‐benzenesulfonamides) ( 6–10 ) and [PdL₂] complexes assembled on multi‐wall carbon nanotubes (MWCNTs) hybrid nanomaterials were fabricated and characterized by various techniques. The [PdL₂] impregnated MWCNTs materials ( 11–15 ) were applied as a counter electrode (CE) catalyst for triiodide to iodide reduction reaction in the dye‐sensitized solar cells (DSSC) and investigated electro‐catalytic activities. The MWCNTs‐supported [PdL₂] CEs ( 11–15 ) are exhibits as Pt‐free CE with good power conversion efficiencies (PCEs), and compared to platinum and bare MWCNTs CEs and the PCE of bare MWCNTs was clearly improved by means of [PdL₂] complexes ( 6–10 ). The DSSCs based on the hybrid counter electrodes (CEs) ( 11–15 ) and bare MWCNTs are indicated a relative efficiency ( ? _rel ) of 64.27%, 54.07%, 53.75%, 51.52% 44.82% and 27.27% concerning a Pt CE control device set at 100%. The report emphasizes that [PdL₂] impregnated MWCNTs type counter electrodes (CEs) ( 11–15 ) are promising as effectively catalyst in working device design, particularly taking into account the eco‐friendly approach of the hybrids.     

Invariant discrete flows

In this paper, we investigate the evolution of joint invariants under invariant geometric flows using the theory of equivariant moving frames and the induced invariant discrete variational complex. For certain arc length preserving planar curve flows invariant under the special Euclidean group , the special linear group , and the semidirect group , we find that the induced evolution of the discrete curvature satisfies the differential‐difference mKdV, KdV, and Burgers' equations, respectively. These three equations are completely integrable, and we show that a recursion operator can be constructed by precomposing the characteristic operator of the curvature by a certain invariant difference operator. Finally, we derive the constraint for the integrability of the discrete curvature evolution to lift to the evolution of the discrete curve itself.     

Heterogeneous copper‐catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β‐keto sulfones

An efficient and practical route to β‐keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM‐41‐supported Schiff base‐pyridine bidentate copper (II) complex [MCM‐41‐Sb,Py‐Cu (OAc)₂] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β‐keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)₂. MCM‐41‐Sb,Py‐Cu (OAc)₂ is also easy to recover and is recyclable up to eight times with almost consistent activity.     

π–π Stacking Interaction in an Oxidized CuII–Salen Complex with a Side-Chain Indole Ring: An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase

In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the Cu^II–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a Cu^II complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized Cu^II complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized Cu^II complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction.