Strain‐Induced Double Carbon–Carbon Bond Activations of Cycloparaphenylenes by a Platinum Complex: Application to the Synthesis of Cyclic Diketones

The carbon–carbon (C?C) bond activation of [n]cycloparaphenylenes ([n]CPPs) by a transition‐metal complex is herein reported. The Pt⁰ complex Pt(PPh₃)₄ regioselectively cleaves two C?C σ bonds of [5] CPP and [6]CPP to give cyclic dinuclear platinum complexes in high yields. Theoretical calculations reveal that the relief of ring strain drives the reaction. The cyclic complex was further transformed into a cyclic diketone by using a CO insertion reaction.     

One-pot synthetic method of unsymmetrical diorganyl selenides: reaction of diphenyl diselenide with alkyl halides in the presence of lanthanum metal

A convenient synthetic method of unsymmetrical selenides has been developed. When diphenyl diselenide was allowed to react with two equimolar amounts of primary alkyl iodides and bromides in the presence of an equimolar amount of lanthanum metal, alkyl phenyl selenides were formed in moderate to good yields. For the reaction of primary alkyl chlorides and secondary alkyl iodides, the yields of the selenides were low; however, the yields were dramatically improved by the addition of TMEDA or HMPA. A reaction pathway involving the generation of a lanthanum phenylselenolate intermediate was suggested.     

Preparation of telechelic oligomers by controlled thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene)

It was found that telechelic isotactic oligo(1-butene) and telechelic oligo(propylene-ran-1-butene) could be isolated as nonvolatile oligomers from polymer residues resulting from the thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene), respectively. Their structures were determined by ¹H and ¹³C NMR with attention being paid to their reactive end groups. The maximum average number of terminal vinylidene groups per molecule (f_TVD) was 1.8, indicating that about 80 mol% were α,ω-diene oligomers having two terminal vinylidene groups. This useful new telechelic oligomer had a lower polydispersity than the original polymer, in spite of its lower molecular weight and T_m. The composition of end groups of nonvolatile oligomers obtained by thermal degradation of poly(propylene-ran-1-butene) could be explained by the differences in bond dissociation energy and activation energy of elementary reactions during thermal degradation, based on the monomer composition of the original polymer.     

In situ x-ray photoelectron spectroscopic and density-functional studies of Si atoms adsorbed on a C60 film

The interaction between C(60) and Si atoms has been investigated for Si atoms adsorbed on a C(60) film using in situ x-ray photoelectron spectroscopy (XPS) and density-functional (DFT) calculations. Analysis of the Si 2p core peak identified three kinds of Si atoms adsorbed on the film: silicon suboxides (SiO(x)), bulk Si crystal, and silicon atoms bound to C(60). Based on the atomic percent ratio of silicon to carbon, we estimated that there was approximately one Si atom bound to each C(60) molecule. The Si 2p peak due to the Si-C(60) interaction demonstrated that a charge transfer from the Si atom to the C(60) molecule takes place at room temperature, which is much lower than the temperature of 670 K at which the charge transfer was observed for C(60) adsorbed on Si(001) and (111) clean surfaces [Sakamoto et al., Phys. Rev. B 60, 2579 (1999)]. The number of electrons transferred between the C(60) molecule and Si atom was estimated to be 0.59 based on XPS results, which is in good agreement with the DFT result of 0.63 for a C(60)Si with C(2v) symmetry used as a model cluster. Furthermore, the shift in binding energy of both the Si 2p and C 1s core peaks before and after Si-atom deposition was experimentally obtained to be +2.0 and -0.4 eV, respectively. The C(60)Si model cluster provides the shift of +2.13 eV for the Si 2p core peak and of -0.28 eV for the C 1s core peak, which are well corresponding to those experimental results. The covalency of the Si-C(60) interaction was also discussed in terms of Mulliken overlap population between them.     

High-resolution scanning tunneling microscopy images of molecular overlayers prepared by a new molecular beam deposition apparatus with spray-jet technique

We developed a new molecular beam deposition apparatus using a spray-jet technique for high-quality thin film preparation of nonsublimable molecules. The apparatus was used to deposit chloro[tri-tert-butyl-subphthalocyaninato]boron(III) (TBSubPc) molecules on an Au(111) surface for analysis by low-temperature scanning tunneling microscopy (STM). Highly resolved images, in which tert-butyl groups in a TBSubPc molecule were clearly identifiable, were obtained. The image quality and the resolution of these images compared favorably well to STM images taken on reference samples which were sublimed onto Au (111) from a heated crucible.     

Viscosities of aqueous solutions of quaternary phosphonium bromides at 15, 25 and 35°C

The viscosities of aqueous solutions of Bu _4-n Ph _n PBr n=0–4 have been measured over the concentration range 0.01–0.2 M at 15, 25 and 35°C, to examine the differences in ion-water interactions of these quaternary cations. The viscosity data were treated by the extended Jones-Dole equation, including the square term in solute concentration, Dc². A decrease in the B coefficient with increase in the number of phenyl groups n, and with increasing temperature is observed. Nearly linear dependence of the B coefficient on n was found, in contrast with partial molal volumes for which non-linear relations with n have been found. D decreases with increasing temperature but becomes independent of n at higher temperatures.     

An electrolytic system based on the anion exchange reaction between KCl and an anion exchange resin

We have developed a novel electrolytic system based on the anion exchange reaction between KCl and Amberlyst A26. It was demonstrated by preparative electrolysis experiments as well as cyclic voltammetry that the anion exchange reaction offers a unique electrolytic system for electroreduction of organic compounds. On the basis of the electrolytic system, electroreduction of aromatic carbonyl compounds was successfully achieved by using an undivided cell to provide the corresponding coupling products as pinacols in good to high yields with high diastereoselectivity.     

Generation of high-contrast and high-intensity laser pulses using an OPCPA preamplifier in a double CPA, Ti:sapphire laser system

We demonstrate a high-contrast, high-intensity double chirped-pulse amplification (CPA) Ti:sapphire laser system using an optical parametric chirped-pulse (OPCPA) pre- amplifier. By injecting cleaned microjoule seed pulses into the OPCPA, a temporal contrast greater than 10¹⁰ within picosecond times before the main femtosecond pulse is demonstrated with an output pulse energy of 1.7 J and a pulse duration of 30 fs, corresponding to a peak power of 60 TW at a 10 Hz repetition rate. This system uses a cryogenically-cooled Ti:sapphire final amplifier and generates focused peak intensities in excess of 10²⁰ W/cm².