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.     

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.     

Proton assisted oxygen-oxygen bond splitting in cytochrome p450

Proton assisted O-O bond splitting of cytochromes' P450 hydroperoxo Compound 0 has been investigated by density functional theory, showing a barrier for the slightly endothermic formation of the iron-oxo Compound I. The barrier and the endothermicity increase with decreasing acidity of the distal proton source. Protonation of the proximal iron heme ligand favors the O-O bond scission and provides an important regulatory component in the catalytic cycle. The Compound 0 --> I conversion is slightly exothermic for the peroxidase and catalase models. Implications of the energetic relationship between the two reactive intermediates are discussed in terms of possible oxidative pathways.     

A `tetrameric' 3,4‐di‐p‐tolyl‐1,2,5‐oxadiborole derivative

In the title compound, 1,1,6a,7,9a,10‐hexa­chloro‐2,3,5,6,8,9,11,12‐octa‐p‐tolyl‐1,6a,9a,12a‐tetraborata‐3a,4a,7,10‐tetrabora‐4a¹,6b,9b,12b‐tetraoxonia‐4‐oxatetra­cyclo­penta­[1,2‐a:2,1,5‐de:1,2‐g:1,2‐i]­naphthalene di­chloro­methane pentasolvate, C₆₄H₅₆B₈Cl₆O₅·5CH₂Cl₂, two condensed oxadiborole rings are attached to two further oxadiborole rings in a type of donor–acceptor bonding, thus forming a ten‐membered alternating (B—O)₅ naphthalene‐like arrangement as the central building block.     

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.     

Synthesis and structures of cationic μ-diborolyl triple-decker complexes [CpCo(1,3-C<Subscript>3</Subscript>B<Subscript>2</Subscript>Me<Subscript>5</Subscript>)M(C<Subscript>5</Subscript>R<Subscript>5</Subscript>)]<Superscript>+</Superscript> (M = Rh or Ir)

The cationic triple-decker complexes [CpCo(1,3-C₃B₂Me₅)M(C₅R₅)]⁺ (M = Rh (2), Ir (3), R = H (a), Me (b)) with the bridging diborolyl ligand were synthesized by the reaction of the sandwich anion [CpCo(1,3-C₃B₂Me₅)]^- (1) with the halide complexes [CpMI₂]₂ or [Cp^*MCl₂]₂ (Cp^* = C₅Me₅). The structures of [2b]PF₆ and [3b]PF₆ were established by X-ray diffraction. The nature of the metal—diborolyl bond in these complexes was analyzed using the energy decomposition scheme.     

η3‐Diphosphavinylcarbene: A P2 Analogue of the Dötz Intermediate

Do the twist : The reaction of in situ generated phosphinidenes with phosphaalkynes is a facile route to the new metal‐coordinated η³‐diphosphavinylcarbene 1 , which shows facile ligand‐exchange reactions and undergoes an unprecedented rearrangement that involves phosphinidene complex 2 and η³‐phosphaalkenylphosphinidene complex 3 , the 1,3 isomer of 1 .