Dramatic rate enhancement of reductive elimination of [Ar‐Pd‐C] was observed in the presence of a phosphine/electron‐deficient olefin ligand. Through systematic kinetic investigations of the Negishi coupling of ethyl 2‐iodobenzoate with alkylzinc chlorides (see scheme), the rate constants for reductive elimination of [Ar‐Pd‐C] were determined to be greater than 0.3 s?1, which is about four or five orders of magnitude greater than values reported previously.
Aluminium speciation : Aluminium speciation in NTf2 ionic liquids has a strong influence on its electrodeposition from the liquid mixture. This work probed the nature of these species and proposes that the electroactive species involved are either [AlCl3(NTf2)]? or [AlCl2(NTf2)2]? (e.g., see figure).
A bicycle built for two : The title reaction affords cis‐fused bicyclo[4.3.0]nonenes from readily available 1,5‐bisallenes with structurally diverse propargylic carbonates and arylboronic acids (see scheme; X=NTs, C(E1)2 with E1=CO2Bn, SO2Ph, dba=trans,trans‐dibenzylidenacetone). The reaction may involve a sequential oxidative addition, two different types of three carbopalladations, and a Suzuki‐type coupling.
Splendid isolation : Monomeric phosphazene F2PN (1A1) was prepared for the first time through irradiation of F2PN3 in an argon matrix with an ArF excimer laser (λ=193 nm). Upon subsequent irradiation with a high‐pressure mercury arc lamp (λ=255 nm), F2PN undergoes a 1,2‐fluorine shift to give iminophosphane cis‐FP?NF.
P makes it possible : The convenient oxidative synthesis of the 16‐electron organophosphorus iron sandwich complex [Fe(η4‐P2C2tBu2)2] (see structure) suggests that the elusive all‐carbon complex [Fe(η4‐C4H4)2] is a viable synthetic target.
Broad spectrum : Novel para‐functionalized aryl‐di‐tert‐butylfluorosilanes, p‐(tBu2FSi)C6H4X (X=functional group), have been made available and broaden the spectrum of silicon‐based 18F acceptors (SiFAs) for potential PET applications. For example, the [18F]maleimido derivative 1 has been employed for the synthesis of [18F] 1 ‐ labeled rat serum albumin (RSA), the applicability of which for PET has been verified by in vivo experiments.
Clicking iron : Cheap and environmentally friendly [Fe(OAc)2] is used for the catalysis of cycloadditions between aryl nitriles and trimethylsilyl azide to prepare substituted 1H‐tetrazoles in good yield (see scheme).
Crossing the bridge : Two isomeric iminofullerenes, [5,6]‐open azafulleroid 1 and [6,6]‐closed aziridinofullerene 2 , were prepared by cycloaddition of an organic azide to C60. These “azalogues” enable the study of the effects of the bridging atom in a fullerene cage, that is, C60‐like (5,6‐open) versus PCBM‐like (6,6‐closed), as a function of their π systems (PCBM=[6,6]‐phenyl‐C61‐butyric acid methyl ester).
Opening the cluster core : Substitution of the chloride ligand in the novel cationic cluster [W3CuS4H3Cl(dmpe)3]+ (see figure; dmpe=1,2‐bis(dimethylphosphino)ethane) by acetonitrile is promoted by water addition. Kinetic and density functional theory studies lead to a mechanistic proposal in which acetonitrile or water attack causes the opening of the cluster core with dissociation of one of the Cu? S bonds to accommodate the entering ligand.
Mix and match : The pentagonal [Mo6O21]n? polyoxomolybdate building block assembles with other sources of Mo, V, and Sb ions to form an orthorhombic Mo‐V‐Sb oxide. The first single‐crystal X‐ray analysis of an orthorhombic Mo–V‐based oxide, a promising catalyst for light alkane selective oxidation known as the “M1 phase”, revealed the structure of the compound.
A pigment of your imagination : A range of polycrystalline solid solutions of a zinc‐rich Znx?1MnxO system (see figure) have been prepared and studied in terms of their colour, diffuse reflectance spectra, Mn valence state and electronic structure. The intense optical absorption arises from Mn2+ doping and is thought to be due to forbidden or partially forbidden transitions between the valence and the conduction band.
Water seeds : Complex stoichiometry/composition and degree of oligomerization (oligomeric supramolecular complex formation) of cucurbit[6]uril (CB[6]) with N‐alkyl‐ and N,N′‐dialkylpiperazine were investigated in aqueous solutions by means of isothermal titration calorimetry (ITC), ESI‐MS, NMR and light scattering measurements.
Sniffing out proteins : Fluorescent DNA G‐quadruplexes have been used for building versatile signaling receptors for proteins in a single solution. Introducing a protein sample to the ensemble results in a unique emission signature for unambiguous identification (see scheme, R=fluorophore). The self‐assembled, pattern‐based protein detection systems are easily fabricated, have the potential for high‐throughput operations, and have the ability to handle small protein samples.
An anti trihydroxycarbenium ion is revealed to be the gas‐phase structure of protonated carbonic acid by IR multiple‐photon dissociation spectroscopy (see picture for calculated structure and comparison of experimental and computed spectra). Deprotonation yields anti‐H2CO3 with a nominal gas‐phase basicity of 724 kJ mol?1.
Enzyme in action : The accumulated single‐molecule image (see picture) of phospholipase A2 (PLA2) 15–21 min after its injection on a lipid membrane shows transient interactions of PLA2 (blue) with the membrane surface and stable binding to the boundaries of membrane structure defects. The adsorbed PLA2 molecules move with a speed below the experimental resolution of 40 nm min?1.
Choosy organomagnesium : Prochiral bis(bromoaryl)alcohols were desymmetrized by treatment with iPr2Mg and an enantiopure Li salt. The resulting arylmagnesium intermediate was trapped with electrophiles. Protonolysis and two follow‐up reactions provided the antihistaminic and anticholinergic drug (R)‐orphenadrine (see scheme).
Broken‐symmetry DFT calculations on transition‐metal clusters with more than two centers allow the hyperfine coupling constants to be extracted. Application of the proposed theoretical scheme to a tetranuclear manganese complex that models the S2 state of the oxygen‐evolving complex of photosystem II yields hyperfine parameters that can be directly compared with experimental data. The picture shows the metal–oxo core of the model and the following parameters; exchange coupling constant Jij, the expectation value of the site‐spin operator , and the isotropic hyperfine coupling parameters.
