Organophosphine/phosphite‐stabilized silver(I) complexes bearing N‐acetylbenzamide ligand: synthesis,characterization and potential application in metal organic chemical vapor deposition

New N‐silver(I) acetylbenzamide complexes of type L_n?AgNC₉H₈O₂ (L = PPh₃; n = 1, 2a; n = 2, 2b; n = 3, 2c; L = P(OEt)₃; n = 1, 2d; n = 2, 2e; n = 3, 2f) were prepared. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³C{H} NMR, ³¹P{H} NMR and IR spectroscopy, respectively. The molecular structure of 2b has been determined by X‐ray single‐crystal analysis in which the silver atom is in a distorted tetrahedral geometry and crystallizes as cis–trans. New N‐silver(I) acetylbenzamide complexes have a four‐membered ring, which could influence their chemical and physical properties and modulate volatility. Metal organic chemical vapor deposition experiments were carried out successfully at 400°C and 450°C using 2e as precursor for the deposition of silver films, respectively. The high‐purity silver film obtained at 400°C is dense and homogeneous. Copyright © 2012 John Wiley & Sons, Ltd.     

Copper‐catalyzed Clauson–Kass pyrroles synthesis in aqueous media

An efficient and convenient copper‐catalyzed Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with amines in aqueous media has been developed, providing a wide range of N‐substituted pyrroles in good yields. It is noteworthy that the Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with p‐phenylenediamine or m‐phenylenediamine proceeds smoothly to afford the corresponding monopyrroles and bispyrroles with high selectivity in impressive yields. A plausible mechanism for the formation of N‐substituted pyrroles has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Copolymerization of styrene and norbornene with β‐diketiminato nickel/methylaluminoxane catalytic system

Styrene–norbornene (S‐N) copolymerizations were carried out using β‐diketiminato nickel complexes CH{C(CF₃)NAr}₂NiBr (Ar = 2,6‐ⁱPr₂C₆H₃, 1 ; Ar = 2,6‐Me₂C₆H₃, 2 ) in the presence of methylaluminoxane. The influence of the comonomer feed content and polymerization temperature on the conversion and composition of the copolymers with the catalytic system was investigated. An increase in the feed ratio of S/N led to an increase in the incorporated styrene content of the resulting copolymer. NMR characterization of the copolymers generated with the catalytic systems showed that the random S‐N copolymers are produced. Differential scanning calorimetric determination of the copolymers shows higher T_g values than polystyrene, and gel permeation chromatographic measurements have shown that the copolymers possess rather narrow molecular weight distributions, suggesting that the copolymerization take place at a single active site. Copyright © 2012 John Wiley & Sons, Ltd.     

Biological evaluation of novel selenazole‐based compounds as potential thioredoxin reductase inhibitors

Recently, thioredoxin reductase as a target for treatment of tumors has attracted the attention of scientists. 1,2‐[Bis(1,2‐benzisoselenazolone‐3(2 H)‐ketone)]ethane (ethaselen, BBSKE, PCT: CN02/00412), designed and synthesized previously, is an effective thioredoxin reductase inhibitor; presently it is in phase II clinical trials, targeting gastric cancer, lung cancer and colon cancer. To seek more novel and effective anticancer drugs, we have developed many selenazole‐based compounds. Evaluation of the thioredoxin reductase inhibitory effect and investigation of the mechanism of anticancer drugs require abundant thioredoxin reductase, but since commercial thioredoxin reductase is expensive its use is often limited. Therefore, the preparation of thioredoxin reductase is necessary. Base on the above investigation, in this work we have prepared thioredoxin reductase and evaluated selenazole‐based compounds, and found that 44 compounds have high inhibitory effect on thioredoxin reductase with IC₅₀ < 10 µ m , of which 16 compounds have IC₅₀ values below 1 µ m . This is helpful in investigating and elucidating the mechanism of this kind of compound. Copyright © 2012 John Wiley & Sons, Ltd.     

Cyclopalladated ferrocenylimine as an efficient catalyst for the syntheses of diarylmethane derivatives

The cyclopalladated ferrocenylimine adducts Ia , Ib , Ic were evaluated in the Suzuki cross‐coupling reaction of benzyl halides with arylboronic acids. The tricyclohexylphosphine adduct Ia exhibited highly catalytic activity for the coupling of aryl and heteroaryl boronic acids containing various functional groups with benzylic bromides and chlorides (up to 99% yield), furnishing diarylmethane derivatives with low catalyst loading (1 mol%). It is worth noting that catalyst Ia can be reused eight times without losing its catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.