ON THE MECHANISM OF PHOTOCHEMICAL ALKYNE INSERTION INTO CYCLOPENTADIENYLIRONDICARBONYL DIMER: ALKYNE ADDITION TO A “TIED-BACK” Cp-Fe DIMER

Abstract

The photochemical insertion of phenylacetylene with the “tied-back” dinuclear complex [(η⁵-C₅H₄)₂SiMe₂]Fe₂(CO)₂(μ-CO)₂ (4) yields, by X-ray structural analysis, a dimetallacyclopentenone product entirely analogous to that obtained from the photochemical reaction of the alkyne with (η⁵ - C₅H₅)₂Fe₂(CO)₂(μ-CO)₂ (1). This result is interpreted as evidence for an alternative pathway for photochemical alkyne addition to 1. Attempts to identify the photochemical intermediates from 4 have been unsuccessful. A competition study between 1 and 4 indicates that photochemical alkyne insertion into 1 is preferred by approximate ratio of 2:1 over insertion into 4.     

Synthesis of oxazole and furan derivatives via Rh2(OAc)4-catalyzed C≡X bond insertion of cyclic 2-diazo-1,3-diketones with nitriles and arylacetylenes

Abstract

A convenient and efficient procedure for the synthesis of 2-substituted-6,7-dihydrobenzo[d]oxazol-4(5H)-ones and 2-aryl-6,7-dihydrobenzofuran-4(5H)-ones through a Rh₂(OAc)₄-catalyzed C≡X (X?=?N, C) insertion of cyclic 2-diazo-1,3-diketones with nitriles and aromatic alkynes has been developed. This reaction uses readily available starting materials and stable cyclic 2-diazo-1,3-diketone compounds, with desired products formed in good to high yields. A tentative mechanism involving a C≡X bond insertion and 1,5-dipolar electrocyclization/ring opening and cyclization sequence for this reaction is proposed.     

Cell Engineering with Functional Poly(oxanorbornene) Block Copolymers

Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of ¹O₂ at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces.     

Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.     

Stereoelectronic Features of a Complex Ketene Dimerization Reaction

The amidation reaction of a tetrahydroisoquinolin-1-one-4-carboxylic acid is a key step in the multi-kilogram-scale preparation of the antimalarial drug SJ733, now in phase 2 clinical trials. In the course of investigating THIQ carboxamidations, we found that propanephosphonic acid anhydride (T3P) is an effective reagent, although the yield and byproducts vary with the nature and quantity of the base. As a control, the T3P reaction of a 3-(2-thienyl) THIQ was performed in the absence of the amine, and the products were characterized: among them are three dimeric allenes and two dimeric lactones. A nucleophile-promoted ketene dimerization process subject to subtle steric and stereoelectronic effects accounts for their formation. Two novel monomeric products, a decarboxylated isoquinolone and a purple, fused aryl ketone, were also isolated, and mechanisms for their formation from the ketene intermediate are proposed.     

郑州市城区悬铃木属(Platanus)树木的瘤突与环境

1996-2006年对郑州市城区悬铃木属(Platanus)树木瘤突进行了实地调查并记录了调查区段汽车过往数量.具瘤突的悬铃木属植株及其瘤突数量逐年上升,瘤突外露体积逐年增大.悬铃木属树木树干基部由地面向上1 m内,是环境汽车尾气致瘤外突的主要部位.事实表明,汽车尾气污染大气环境,致使城区环境日趋劣化,直接威胁着绿色植物的正常生长与人类健康.     

Cyclopentadienyl rhodium(III) complexes as catalysts for the insertion of phenyldiazoacetate into E−H bonds

Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal.     

Solution Phase Reactivity of Dibenzo[c,e][1,2]azaborinine: Activation and Insertion into Si-E Single Bonds (E=H,OSi(CH3)3, F,Cl) by a BN-Aryne

The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond.     

Effect of the ZnNi y Mn2– y O4 (0 ≤ y ≤ 1) spinel composition on electrochemical lithium insertion

The electrochemical insertion of lithium in the spinel-type manganite with the formula ZnNi _y Mn_{2– y} O₄ has been studied. The galvanostatic discharge curves show that the best performance is obtained for y = 0.25, where a tetragonal to cubic structural transformation occurs. The thermodynamics and kinetics of the process of insertion of the lithium into the tetragonal spinel Li _x ZnNi_0.25Mn_1.75O₄ (x = 0.05–1.3) have been studied. The molar thermodynamic quantities, such as enthalpy, entropy and free energy determined by EMF-T measurements, varied with the lithium concentration in the oxide structure, and a major variation was observed around x = 0.8. The chemical diffusion coefficient of lithium in these spinels was also determined. Structural analysis, degree of oxidation and magnetic susceptibility measurements were carried out for the lithiated oxides in order to obtain the cationic distribution as a function of x. It has been possible to demonstrate that, upon lithium insertion, Mn⁴⁺ ions on B sites are reduced to Mn³⁺ and then to Mn²⁺. A cooperative Jahn-Teller effect is present in these spinel manganese-nickel oxides. Received: 4 February 1997 / Accepted: 11 April 1997     

Multilayer Porous Vanadium Nitride Microsheets Anodes for Highly Stable Na-ion Batteries

Sodiumion batteries(SIBs)have attracted intensive attention as promising alternative to lithium-ionbatteries(LIBs)for large scale energy storage systems because of low cost of sodium,similar energy storage mechanism and the reasonable performance.However,it is still a great challenge to search and design a robust structure of anode materials with excellent cycling stability and high rate capability for SIBs.Herein,multilayer porous vanadium nitride(VN)microsheets are synthesized through a facile and scalable hydrothermal synthesis-nitrogenization strategy as an effective anode material for SIBs.The multilayer porous VN microsheets not only offer more active sites for fast Na+insertion/extraction process and short diffusion pathway,but also effectively buffer the volume change of anode due to more space in the multilayer porous structure.The large proportions of capacitive behavior imply that the Na+charge storage depends on the intercalation pseudocapacitive mechanism.The multilayer porous VN microsheets electrodes manifest excellent cycling stability and rate capability,delivering a discharge capacity of 156.1 mA·h/g at 200 mA/g after 100 cycles,and a discharge capacity of 111.9 mA·h/g at 1.0 A/g even after 2300 cycles with the Coulombic efficiency of nearly 100%.