Measurements on diproton emission from the break-up channels of 23Al and 22Mg

Two-proton relative momentum distributions from the break-up channels ²³Al→p+p+²¹Na and ²²Mg→p+p+²⁰Ne at an energy of 60–70 A MeV have been measured together with two-proton opening angles at the projectile fragment separator beamline (RIPS) in the RIKEN Ring Cyclotron Facility. The results demonstrate the existence of diproton emission component from single-step ²He for highly excited ²³Al and ²²Mg.     

Infrared studies of stereoregular polymerization of methyl methacrylate and methacrylonitrile by organometallic compounds

Infrared spectra of reaction mixtures of methyl methacrylate or methacrylonitrile with an equimolar amount of organometallic compounds were investigated in relation to the stereoregulating ability of the catalysts in polymerization. It was found that the carbonyl or nitrile stretching frequency correlated with the stereoregularity of polymers prepared with the corresponding catalysts; i.e., the higher the frequency, the higher the isotacticity. From these results a mechanism of isotactic polymer formation was proposed, in which catalyst counterion was located near the carbonyl group in polymer terminal and that of monomer to be reacted, and consequently the isotactic polymerization is facilitated.     

Investigation of the angular dependence of the analyzing powers in the deuteron-proton elastic scattering at the nuclotron

New polarimeter based on the asymmetry measurement in dp-elastic scattering has been constructed at internal target at Nuclotron (JINR). The result on the deuteron analyzing powers A _y , A _yy and A _xx in the deuteron-proton (dp) elastic scattering at the energies of 880 and 2000 MeV are presented. They are compared with different theoretical approaches.     

Spin physics in few body systems at Nuclotron

The review of the recent results on spin effects in few nucleon systems obtained at LHEP-JINR are presented. The data on the deuteron analyzing powers in different reactions in the wide energy range demonstrate the sensitivity to the spin structure of the light nuclei. The future plans on the studies with polarized deuterons from new polarized ion source at Nuclotron will be reported.     

Chloride‐Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins

Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride‐bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]₂, chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)‐prop‐1‐ene‐1,2‐diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.     

Rare-earth silylamide-catalyzed monocoupling reaction of isocyanides with terminal alkynes

[reaction: see text] Rare-earth silylamides, Ln[N(SiMe3)2]3 (Ln = Y, La, Sm, Yb), serve as good catalysts for monoinsertion of isocyanides into terminal alkynes in the presence of amine additives, leading to 1-aza-1,3-enyens in excellent yields. The reaction is applicable to a diverse set of terminal alkynes with various functionalities such as ethers, acetals, and amino groups. Larger metals (La and Sm) give a better performance than smaller ones (Y and Yb). Using less hindered primary amines and, in contrast, bulky isocyanides is crucial for the coupling reaction; otherwise, competitive oligomerization of the isocyanides occurs predominantly. In the mechanistic study, the rate-determining step of the reaction seems to be the first insertion of the isocyanides into rare-earth alkynides, which is followed by spontaneous protonation with the amine additives.     

Chirality transfer during alkylation of chiral amides

Chiral amides derived from O-methyl mandelic acid and achiral amines underwent enantioselective alpha-methylation on treatment with LTMP followed by addition of methyl iodide; chirality transfer from an undeprotonated chiral amide into an achiral enolate in a mixed aggregate is supposed to be responsible for the asymmetric induction.     

Electron transfer of conjugated polymeric ferrocenes

This paper describes three topics on the π‐conjugated ferrocene oligomers and polymers; the first is the dependence of intervalence‐transfer bands for mixed‐valence oligo(1,1'‐dihexylferrocenylene)s on the oxidation number and the number of ferrocene units, the second is synthesis of azo‐bridged ferrocene oligomers and a polymer and electrochemical and optical analysis of internuclear electronic interactions in their mixed‐valence states and the third is synthesis, redox behaviors and electrodeposition of oligoferrocenylene‐modified gold clusters.