The triangular clusters [Zn3Cp*3](+) and [Zn2CuCp*3] were obtained by addition of the in situ generated, electrophilic, and isolobal species [ZnCp*](+) and [CuCp*] to Carmona's compound, [Cp*Zn-ZnCp*], without splitting the ZnZn bond. The choice of non-coordinating fluoroaromatic solvents was crucial. The bonding situations of the all-hydrocarbon-ligand-protected clusters were investigated by quantum chemical calculations revealing a high degree of σ-aromaticity similar to the triatomic hydrogen ion [H3](+). The new species serve as molecular building units of Cu(n)Zn(m) nanobrass clusters as indicated by LIFDI mass spectrometry.

Zinc–zinc interactions on nickel and palladium centers are highly dependent on the co-ligands. These dependencies are also found for the formation of dihydrogen vs. dihydride complexes and underline the analogy [Zn2Cp*2] ↔ H2.

Addition of a modulator in the LPE process enhances MOF thin film properties by boosting their crystallinity, orientation uniformity, and adsorption capacity.

Organolithium compounds are amongst the most important organometallic reagents and frequently used in difficult metallation reactions.H owever,t heir direct use in the formation of C À Cbonds is less established. Although remarkable advances in the coupling of aryllithium compounds have been achieved, Csp 2 ÀCsp 3 coupling reactions are very limited. Herein, we report the first general protocol for the coupling or aryl chlorides with alkyllithium reagents.P alladium catalysts based on ylide-substituted phosphines (YPhos) were found to be excellently suited for this transformation giving high selectivities at room temperature with avariety of aryl chlorides without the need for an additional transmetallation reagent. This is demonstrated in gram-scale synthesis including building blocks for materials chemistry and pharmaceutical industry.Furthermore,the direct coupling of aryllithiums as well as Grignard reagents with aryl chlorides was also easily accomplished at room temperature.

Reactions of homoleptic isonitrile ligated complexes or clusters of d(10)-metals with the potent carbenoid donor ligand GaCp* are presented (Cp* = pentamethylcyclopentadienyl). Treatment of [Ni4(CNt-Bu)7], [{M(CNR)2}3] (M = Pd, Pt) and [Pd(CNR)2Me2] (R = t-Bu, Ph) with suitable amounts of GaCp* lead to the formation of the heteroleptic, tri- and tetranuclear clusters [Ni4(CNt-Bu)7(GaCp*)3] (1), [{M(CNt-Bu)}3(GaCp*)4] (M = Pd: 2a, Pt: 2b), and [{Pd(CNR)}4(GaCp*)4] (R = t-Bu: 3a, Ph: 3b). The reactions involve isonitrile substitution reactions, GaCp* addition reactions, and cluster formation reactions. The new compounds were investigated for their ability to undergo Ga/Zn exchange reactions when treated with ZnMe2. The novel tetranuclear Zn-rich clusters [Ni4GaZn7(Cp*)2Me7(CNt-Bu)6] (4) and [{Pd(CNR)}4(ZnCp*)4(ZnMe)4] (R = t-Bu: 5a, Ph: 5b) were obtained and isolated. The electronic situation and geometrical arrangement of atoms of all compounds will be presented and discussed. All new compounds are characterized by solution (1)H, (13)C NMR and IR spectroscopy, elemental analysis (EA), liquid injection field desorption ionization mass spectrometry (LIFDI-MS) as well as single crystal X-ray crystallography.