No need for a metal : A combination of mass spectrometry and computational studies (density functional theory and coupled‐cluster methods) shows that [P4O10].+ is the first polynuclear nonmetal oxide cation that is capable of activating the C? H bond of methane at room temperature (see picture). This process represents a further example in the reactivity of oxygen‐centered radicals.
?The biggest challenge facing scientists is finding a way to make clean energy. If I could have dinner with three famous scientists from history, they would be Marie Curie, Dmitri Mendeleev, and Henri Moissan. …?“ This and more about Véronique Gouverneur can be found on page 3559.
What's the matter? The laboratory Raman spectra for carbonic acid (H2CO3), both for the β‐polymorph and its amorphous state, are required to detect carbonic acid on the surface of the pole caps of Mars in 2009, when the Mars Microbeam Raman Spectrometer lands on the planet. The picture shows a martian crater with ice of unknown composition, possibly containing carbonic acid (image adapted from DLR, with permission from ESA, DLR, and FU Berlin –‐G. Neukum).
Bridging or pendant? Palladium and rhodium complexes deriving from an ambiphilic phosphine–borane ligand are shown to adopt a bridging P→M? Cl→B coordination mode in the solid state. DFT calculations provide more insight into the Cl→B interaction and suggest the possible interconversion of the bridging and B‐pendant forms in solution.
Linked to the Pentagon : The addition of molybdate to [HBW11O39]8? ions leads to the formation of mixed pentagonal units {W(Mo5)} and {W(WMo4)} trapped as linkers in the resulting modular assemblies, thus establishing the first link between the conventional Keggin ion derivatives and the giant molybdenum oxide and keplerate ions.
Custom built : A promising new approach towards more efficient self‐assembled cage receptors through computer‐aided design is demonstrated. The resulting M4L6 tetrahedral cage, internally functionalized with accurately positioned urea hydrogen‐bonding groups (see structure; yellow: predicted, blue: experimental, space‐filling: SO42?), proved to be a remarkably strong sulfate receptor in water.
Sleeping beauty? Is the scientific community about to kiss awake iron catalysis, a topic that has been dormant for decades? A recent study on a user‐friendly direct cross‐coupling reaction of alkyl and aryl halides constitutes an important step toward this end through the integration of two different iron‐catalyzed elementary steps into a practical one‐pot procedure.
Hooking up : FeCl2 catalyzes the efficient cross dehydrogenative arylation of substrates having benzylic C? H bonds (see scheme). High regioselectivity was observed during the cross‐coupling between compounds containing aromatic C(sp2)? H bonds and benzylic C(sp3)? H bonds. This process is proposed to proceed by single‐electron‐transfer oxidation and Friedel–Crafts alkylation.
Surprisingly stable : Noble‐metal complexes with terminal oxo ligands are frequently postulated as intermediates, but they are generally considered elusive, as their d electrons destabilize the M?O units. Until recently, the isolation of such compounds was thought to require strong acceptor ligands, but now a remarkably stable Pt?O complex has been obtained employing a simple pincer ligand.
Caught in the act : An alkyl alkene ZrIV complex (see picture; Cp=C5H5) has been synthesized and characterized for the first time. The alkene bonding mode is highly asymmetric, and C2 is quite carbocationic. There is also evidence for rotation about the C1? C2 bond. This extremely unusual complex provides an exemplar of previously unknown intermediates in Ziegler–Natta and carbocationic polymerization reactions of alkenes.
Electron by electron : β‐Diketiminato nickel(I) complex fragments are capable of activating N2 through coordination. The resulting complex can be reduced in two single‐electron steps, which further activates the N? N bond. The picture shows the structure of the singly reduced complex with μ‐η1:η1‐bound N2.
Without the need for organohalide precursors , the convenient and general synthesis of aryl (or diaryl) sulfides can be achieved by using aryl carboxylic acids and thiols or disulfides for decarboxylative C? S cross‐coupling catalyzed by a bimetallic system (see scheme).
The silene (Me3Si)2Si?Ad is polymerized to produce a polycarbosilane with an unusual Si? Si? C repeating backbone, rather than the Si? C or Si? Si? C? C units expected for olefinic radical polymerization. The polymer structure and the polymerization mechanism (see scheme) were studied by GPC, EPR, and NMR spectroscopy and by trapping experiments.
Oxidizing gold? A gold(I)/gold(III) catalytic cycle is essential for the first oxidative cross‐coupling reaction in gold catalysis. By using Selectfluor for gold(I) oxidation, this chemistry reveals the synthetic potential of incorporating gold(I)/gold(III) catalytic cycles into contemporary gold chemistry and promises a new area of gold research by merging powerful gold catalysis and oxidative metal‐catalyzed cross‐coupling reactions.
Synergy in synthesis : Strategic consideration of metathesis and Suzuki–Miyaura (SM) cross‐coupling for C? C bond‐formation processes has opened up new and “green” synthetic routes to various complex targets. The use of this synergistic combination for the synthesis of supramolecular ligands, polyaromatic compounds, and complex natural products is covered in this Focus Review.
Perlen auf Gold : Neuartige multifunktionelle Nanopartikel bestehen aus einzelnen Amin‐modifizierten Goldnanostäbchen, an denen Fe3O4‐„Perlen“ mit Carboxyendgruppe angebracht sind. Die Partikel eignen sich zur simultanen Erkennung, dualen Bildgebung und photothermischen Ablation von Brustkrebszellen.
Amorphization tunes acidity : Pseudo‐bridging silanols, suggested as versatile Brønsted acid groups by molecular modeling studies, are obtained by shifted hydrolysis of Si? O? Al bridges formed by the thermal treatment of silica deposited on γ‐Al2O3 (100), and appear under given pretreatment conditions. Demixing of part of the silica from the aluminosilicate phase is predicted upon excess water adsorption.
