Self‐assembled coordination cages are interesting as drug‐delivery systems. Therefore, the synthesis of new M2L4 (M = Pd, Pt) molecular cages derived from highly fluorescent, rigid polyaromatic ligands is reported herein, and the first Pt2L4 cage with a ligand consisting of three pyridine moieties is described. The photophysical properties were examined, and they showed high quantum yields Φ of up to 48 % for the methoxy‐functionalized ligands. Coordination of the ligands to palladium and platinum ions did, however, reduce the fluorescence of the metallocages. The host–guest chemistry of the palladium cages with cisplatin was investigated, which confirmed the encapsulation. The cages encapsulating cisplatin show significantly increased cytotoxicity towards A549 (human lung adenocarcinoma) cells relative to that shown by cisplatin and, thus, appear to be promising delivery vectors for the anticancer drug cisplatin.

The first stable formal Cu(iii) NHC and its unusual reactivity with acetate are reported. Several products of this reaction are identified and fully characterised. It reactivity is extensively investigated and additionally explored by means of theoretical, electrochemical and isotope labelling experiments.

In this work, cluster expansion of nine-atomic germanium clusters with nickel and platinum atoms is reported. The compounds [(Me3Si)3­Si]3­Et­[Ge9Ni]­(PPh3) and [(Me3Si)3­Si]3­Et­[Ge9Pt]­(PPh3) are characterized by NMR spectroscopy, elemental analysis, and single crystal X-ray structure analysis. The latter represents the first intermetalloid Ge-Pt cluster with a platinum atom as part of a deltahedron. So far, only one compound of this type has been reported for the homologous Pd. Hence, with these new compounds, metal-coordinated deltahedral Ge9 clusters are now known for the whole triad of group 10 elements. The cluster compounds are accessible by treating [(Me3Si)3­Si]3­EtGe9 with η2-ethylene-bis-(triphenyl­phos­phine)-nickel­(0) and η2-ethylene-bis-(triphenyl­phos­phine)-platinum­(0), respectively, in toluene. The crystal structure determination reveals ten-vertex-closo-[Ge9 M]-cluster cores (M = Ni, Pt) bearing five exo-bonded ligands. Unlike the nine-vertex-cluster [(Me3Si)3­Si]3­EtGe9, the penta-functionalized platinum containing cluster compound [(Me3Si)3­Si]3­Et­[Ge9Pt]­(PPh3) does not show fluctuating behavior in solution over a wide temperature range on the NMR time scale, whereas the [(Me3Si)3­Si]3­Et­[Ge9Ni]­(PPh3) shows highly dynamic processes in solution at ambient temperature.

We introduce a large-scale synthesis of a sterically encumbered N-heterocyclic olefin (NHO) and illustrate the ability of its deprotonated form to act as an anionic four-electron bridging ligand. The resulting multicenter donating ability has been used to link two low oxidation state Ge(II) centers in close proximity, leading to bridging Ge−Cl−Ge and Ge−H−Ge bonding environments supported by Ge 2 C 2 heterocyclic manifolds. Reduction of a dimeric [RGeCl] 2 species (R = anionic NHO, [(MeCNDipp) 2 C CH] − ; Dipp = 2,6-i Pr 2 C 6 H 3 ) did not give the expected acyclic RGeGeR analogue of an alkyne, but rather ligand migration/disproportionation transpired to yield the known diorganogermylene R 2 Ge and Ge metal. This process was examined computationally, and the ability of the reported anionic NHO to undergo atom migration chemistry contrasts with what is typically found with bulky monoanionic ligands (such as terphenyl ligands).

Invited for the cover of this issue is the group of Fritz Kühn from Technische Universität München, Germany. The cover image shows a palladium cage encapsulating cisplatin, represented by a bowling ball, knocking down the pins, which symbolize cancer cells.

No abstract

A new pyridine functionalized N-heterocyclic silane with ambident reactivity as a ligand has been synthesized and characterized by NMR spectroscopy ( 1 H, 13 C{ 1 H}, 29 Si), mass spectrometry, elemental analysis, and X-ray crystallography. This ligand reacts with iridium and rhodium cod precursors (cod = 1,5-cyclooctadiene) to yield two new complexes that possess divergent, and unexpected, binding properties. In particular, no oxidative addition occurs at the intraligand Si-H unit. With the iridium(I) center, the ligand acts as a tertiary amino-pyridine chelator, whereas coordination of rhodium(I) to the ligand occurs with arene πcomplexation on an opposite side. The latter interaction yields an unprecedented, electronically induced, coordination change at the silicon center over a long spatial distance. The new iridium and rhodium compounds are of high interest as they provide two potentially different reactions sites in one complex and as these sorts of complexes are known to activate small molecules like dihydrogen or silanes. Hence, the compounds are promising candidates for applications in tandem catalysis. Furthermore, the rhodium complex might be utilized for molecular switches, sensors, and comparable applications.

100% atom economy, 15 examples, yields up to 98%, high regioselectivity, good functional group tolerance.