Proof‐of‐principle is reported for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of hybrid compounds containing (M)/T/E semi‐conductor nodes (M=Cu; T=Ge, Sn; E=S). In their Full Paper on page 6595 ff. , S. Dehnen et al. show how it is possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COMe ligands into CR(N–NH2) or CR(N–NHPh) terminal groups by reaction of a series of novel, functionalized thiometallate cages [(RT)nSm] (n/m=4/6, 3/4), the R ligands of which are terminated by COO(H) or COMe.
Complete exchange : [M6X12] type cluster compounds with an octahedral M6 metal atom arrangement, which is completely surrounded by alcoholato ligands, were unknown until now. The first representatives are prepared containing a [Nb6(OR)12]4+ unit (R=CH3 or C2H5). They are accessible at elevated temperatures from strongly basic alcoholate solutions of [Nb6Cl12]2+‐containing precursors. C gray, H white, K turquoise, Nb blue, O red.
Three that matter : Metal acetylides from alkyl propiolates allow C3 homologations with transference of their versatile reactivity profile to products that can then react without further elaboration. Metal‐free acetylides, which are generated by the action of a good nucleophile on the alkyl propiolate, react with suitable electrophiles through different domino reactions to generate skeletal diversity.
Under pressure : The changes occurring in [Co2(CO)6(XPh3)2] species at high pressure and low temperature have been investigated by experimental X‐ray diffraction and ab initio periodic calculations. The transformation of the carbonyl conformation (from staggered to eclipsed; see figure) and the compression/expansion of the Co? Co bond have been carefully analysed.
A special advantage : The platinum(II)‐catalyzed tandem cyclization of aminoalkynes with 1,3‐diketones offers a new and highly efficient method for the synthesis of indolines and tetrahydroquinolines (see scheme; M.S.=molecular sieves). This transformation affords good to excellent product yields with high regio‐ and chemoselectivity under mild reaction conditions.
Acid remarks : The anhydrous diprotic boron acids H2(B12X12) (X=Cl, Br; see picture, B orange, X green) are the first examples of diprotic superacids and may be the strongest acids yet isolated. Both protons protonate benzene to give benzenium ion salts that are stable at room temperature. These acids owe their existence to the stability of the icosahedral B12 cluster with its dinegative charge buried beneath a layer of halide substituents.
Metal‐stabilized belts : A torus, 3 , consisting of three four‐ and three eight‐membered conjugated rings and stabilized by (RCp)Co‐ and (RCp)Rh‐ units, was generated by irradiation of [(RCp)Co(CO)2] and [(RCp)Rh(C2H4)2], respectively, and 1 .
Caged chalcogens : A series of novel, functionalized TnSm cages (T=Ge, Sn; n/m=4:6, 3:4) with terminal COO(H) or COMe groups were synthesized and show further reactivity toward CuI complexes (an example of which is shown here) and to hydrazines. This led to the generation of functionalized Cu/T/S clusters or the formation of Schiff bases at the C?O groups, respectively, with or without further fragmentation of the T/S core.
Functionalized nanodiamonds : Various functional groups have been incorporated into the structures of the naturally occurring diamondoids [1(2)3]tetramantane and [12312]hexamantane (cyclohexamantane), which represent hydrogen‐terminated prism‐shaped nanodiamonds (see picture). The attachment points define the use of these diamond‐like molecules as geometric building blocks for a variety of applications.
Welcome to the family! The constitution of the chiral D2‐C80 fullerene has been confirmed through single‐crystal X‐ray analysis of the chlorinated C80Cl12. The addition pattern of the chlorine atoms in the structure of C80Cl12 together with other structures of halogenated higher fullerenes is discussed. A stepwise principle of higher fullerene reactivity is proposed. Unusual short intermolecular chlorine–chlorine contacts are reported.
Two dragons playing ball : Direct metal–metal bond formation using a π‐conjugated dinuclear metalladithiolene complex with two electron‐deficient metal centers as building blocks led to a cyclic double trinuclear heterometalladithiolene cluster with two parallel plane bridges (see structure; Rh pink, Mo green, S yellow, C gray, O red).
Lighting up new platinum anticancer complexes : Photoactivation of a platinum(IV) diazido anticancer complex in the presence of a derivative of imidazole, an important constituent of biomolecules, gives surprising photoproducts, including a tetrakis imidazole platinum(II) adduct (see figure), together with free azide, dioxygen and ammonia.
Alcohol oxidation and self‐assembly: the in situ oxidation of hydroxyl functional groups to quinone groups promotes the formation of enhanced hydrogen bonds and allows reorganization of the resulting supramolecular self‐assemblies, which evolve from a weakly bound dense phase to a strongly bound nanoporous open structure (see picture).
Weak and robust ? Tetraalkylammonium salts of weakly coordinating fluorinated alkoxyaluminates are easily accessible, chemically robust materials that show interesting physico‐chemical properties like low melting points, high electrochemical stability and electric conductivity in weakly polar solvents such as CH2Cl2, Ph‐F and toluene.
Towards polythiophene polyrotaxanes : The β‐substituted terthiophene [2]rotaxanes have been synthesized (see figure). Basic optical and electrochemical properties of the synthesized [2]rotaxanes are also reported.
Si takes a rest : A bulky σ‐bound terphenyl substituent and a π‐bound Cp* ligand enable the isolation and full characterization of the first aryl‐substituted, monomeric silicon(II) compound 1 , which can be regarded as the “resting state” of a true silylene containing a σ‐bound Cp* group. The conformation of the aryl group prevents aryl–Si π back‐bonding.
Designing superacids: A computational study of protonated boratabenzenes and the gas‐phase acidity of their conjugate acids is presented. Conjugate acids of boratabenzenes substituted with CN or CF3 groups (see figure) are highly acidic species; the protonated hexacyanoboratabenzene and hexakis(trifluoromethyl)boratabenzene have computational gas‐phase acidities of 250.5 and 276.8 kcal mol?1, respectively.
