Chiral-at-Molybdenum – A Computational Study on N-Substituted cis-MoO2(nacnac)2

Cis-MoO₂(nacnac)₂ (nacnac=β-diketiminate) can be a viable chiral-at-metal catalyst when its two β-diketiminate (nacnac) ligands are N-substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây-Dutt, Conte-Hippler, and Dhimba-Muller-Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X-D/6-311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔG^o=27.4 kcal/mol with N-substituted t-butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed.     

Strategies for Probing P-Parity Violation in Nuclear Collisions at the NICA Accelerator Facility

Physics of Particles and Nuclei Letters - Possible approaches to experimentally detecting P-parity violation in polarized proton or deuteron interactions with an unpolarized target are discussed....     

Neutral palladium(II) complexes with P,N Schiff-base ligands: Synthesis, characterization and catalytic oligomerisation of ethylene

New N-functionalised 2-phosphinobenzaldimino (P^N) ligands bearing 3-picolyl, furfuryl, thiophene-2-methyl, thiophene-2-ethyl, and benzyl groups have been prepared in good yield. The 2-phosphinobenzaldimino ligands were reacted with PdCl₂(COD) to give the corresponding metal complexes of the type Pd(L)Cl₂ (L = 2-phosphinobenzaldimino (P^N) ligand). All compounds were fully characterized using spectroscopic and analytical techniques, including ¹H, ¹³C, and ³¹P NMR and IR spectroscopies, mass spectrometry and elemental analysis. Selected neutral palladium complexes were evaluated as catalyst precursors in ethylene oligomerisation reactions, after activation with a co-catalyst (MMAO, EtAlCl₂, or Et₂AlCl).     

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3‐P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X‐ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht=tetrahydrothiophene) gives a unique P‐bridged gold trimer, while a P,N‐bidentate complex results from [{RhCl(cod)}₂]. The nitrilium ion methodology allows extension of the 1,3‐P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β‐diketiminate ligand.     

The VEPP-2000 electron-positron collider: First experiments

In 2007, at the Institute of Nuclear Physics (Novosibirsk), the construction of the VEPP-2000 electron-positron collider was completed. The first electron beam was injected into the accelerator structure with turned-off solenoids of the final focus. This mode was used to tune all subsystems of the facility and to train the vacuum chamber using synchrotron radiation at electron currents of up to 150 mA. The VEPP-2000 structure with small beta functions and partially turned-on solenoids was used for the first testing of the “round beams” scheme at an energy of 508 MeV. Beam-beam effects were studied in strong-weak and strong-strong modes. Measurements of the beam sizes in both cases showed a dependence corresponding to model predictions for round colliding beams. Using a modernized SND (spherical neutral detector), the first energy calibration of the VEPP-2000 collider was performed by measuring the excitation curve of the phimeson resonance; the phi-meson mass is known with high accuracy from previous experiments at VEEP-2M. In October 2009, a KMD-3 (cryogenic magnetic detector) was installed at the VEPP-2000 facility, and the physics program with both the SND and LMD-3 particle detectors was started in the energy range of 1–1.9 GeV. This first experimental season was completed in summer 2010 with precision energy calibration by resonant depolarization.     

Bisphosphine‐Functionalized Cyclic Decapeptides Based on the Natural Product Gramicidin S: A Potential Scaffold for Transition‐Metal Coordination

The natural product Gramicidin S is a promising scaffold for novel oligopeptide‐based bisphosphine ligands, combining the advantageous rigid chiral backbone with the close proximity of phosphine substituents. The required unnatural, phosphine‐containing, amino acid building blocks were synthesized by means of a novel protocol that involves the enantioselective alkylation of a chiral nickel Schiff base template. Three Ni complexes were prepared with different alkyl chains between the phosphine group and the α‐carbon atom of the incorporated glycine; the absolute stereochemistry of two of them was determined by single‐crystal X‐ray structure analysis. By detaching the template, enantiopure L ‐phosphine amino acids resulted enabling the solid‐phase, stepwise construction of a linear sequence of the phosphine‐modified oligopeptides. On cyclization three bisphosphine‐substituted Gramicidin S analogues resulted, differing only in the size and shape of the linkage between the phosphine groups and the oligopeptides backbone. Their crystal structures suggest these species to have potential as chelating ligands.     

Preliminary results of the cross-section measurement of e<Superscript>+</Superscript>e<Superscript>−</Superscript> → φ(1020)η process with the CMD-3 detector at VEPP-2000 collider

We report preliminary results on the cross section of the process e⁺e^? → φ(1020)η measured at 30 center-of-mass energy points in the range from 1.59 up to 2.0 GeV. Data analysis is based on the integrated luminosity of 22 pb^?1 collected with the CMD-3 detector in 2011–2012. The obtained cross section agrees with the BaBar measurement and has better statistical accuracy.