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.

The first example of ligand protected Cu-Zn clusters is described. Reaction of [CpCu(CN(t)Bu)] with [Zn2Cp*2] yields [(CuCN(t)Bu)4(ZnCp*)4] (1a) and [(CuCN(t)Bu)4(ZnCp*)3(ZnCp)] (1b). According to DFT calculations, the [Cu4Zn4] unit fulfils the unified superatom model for cluster valence shell closing.

Inseparable zinc pair: The reaction of homoleptic {GaCp*}‐containing compounds [M(GaCp*)4] (M=Pd, Pt; Cp*=Me5C5) with [Zn2Cp*2] leads to the formation of [M(GaCp*)2(ZnCp*)2(ZnZnCp*)2] (see picture: C gray, Ga yellow, Zn green, Pd blue) and [M(ZnCp*)4(ZnZnCp*)4]. Both molecules involve the novel zinc ligand system {ZnZnCp*}, which contains an intact ZnZn bond.

Zn-Cp* bond cleavage reactions leading to novel monovalent cationic zinc species are presented (Cp* = pentamethylcyclopentadienyl). The treatment of [Zn2Cp*2] with two equiv. of [H(Et2O)2][BAr4(F)] (BAr4(F) = B{C6H3(CF3)2}4) yields the triple-decker complex [Cp*3Zn4(Et2O)2][BAr4(F)] (1) via protolytic removal of a Cp* ligand as Cp*H, whereas the reaction with an equimolar amount of [FeCp2][BAr4(F)] (Cp = cyclopentadienyl) results in the formation of [Cp*Zn2(Et2O)3][BAr4(F)] (2) under oxidative cleavage of a Cp* ring giving decamethylfulvalene, (Cp*)2, and [FeCp2] as by-products. The molecular structures of compounds 1 and 2 are established by single-crystal X-ray diffraction studies. A new synthetic pathway for the formation of [Zn2Cp*2] based on the reductive elimination of Cp*H from in situ formed Cp*ZnH is presented.

Substitution reactions of labile d10 metal starting complexes with [Zn2Cp*2] (Cp* = pentamethylcyclopentadienyl) are presented. The treatment of [M(cod)2] (M = Ni, Pt; cod =1,5-cyclooctadiene) with stoichiometric amounts of [Zn2Cp*2] results in the formation of [Cp*M(ZnCp*)3] (M = Ni (1), Pt (2)) with the release of 1,3-cyclooctadiene. In addition to Cp* transfer reactions from zinc(I) to the transition-metal centers, the formation of compounds 1 and 2 results via redox chemical pathways: namely, the oxidation of M(0) to M(I) and the reduction of 1 equiv of Zn(I) to Zn(0). The Pd homologue [Cp*Pd(ZnCp*)3] (3) is obtained as a byproduct in the reaction of [Pd(CH3)2(tmeda)] (tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine) with [Zn2Cp*2]. Herein, various side reactions and competing redox chemical processes are involved, including the formation of [Pd(ZnCp*)4(ZnMe)4] as well as [Pd(ZnCp*)4(ZnMe)2(Zn{tmeda})]. Compounds 1–3 have been fully characterized by single-crystal X-ray diffraction, 1H and 13C NMR spectroscopy, IR spectroscopy, and liquid injection field desorption ionization mass spectrometry (LIFDI-MS).

When the dinuclear Ru precursor [Ru(OOCCH)] is employed under redox-inert conditions, a Ru analogue of HKUST-1 was successfully prepared and characterized as a phase-pure microcrystalline powder. X-ray absorption near-edge spectroscopy confirms the oxidation state of the Ru centers of the paddle-wheel nodes in the framework. The porosity of 1371 m/mmol of Ru-HKUST-1 exceeds that of the parent compound HKUST1 (1049 m/ mmol).

The synthesis and characterization of the cationic mixed metal Ga/Zn cluster [Zn2(GaCp*)6](2+) (1) is presented. The reaction of [Zn2Cp*2] with [Ga2Cp*][BAr4(F)] leads to the formation of the novel complex being the first example of a [Zn2](2+) core exclusively ligated by metalloid group-13 organyl-ligands. Compound 1 exhibits two different coordination modes: In the solid state, two of the six GaCp* ligands occupy bridging positions, whereas VT (1)H NMR indicates the coexistence of a second isomer in solution featuring six terminal GaCp* ligands. Quantum chemical calculations have been carried out to assign the gallium and zinc positions; the bonding situation in 1 is characterized and the importance of dispersion forces is discussed.