Interdependence between nanoclusters AuAg24 and Au2Ag41

Whole series of nanoparticles have now been reported, but probing the competing or coexisting effects in their synthesis and growth remains challenging. Here, we report a bi-nanocluster system comprising two ultra-small, atomically precise nanoclusters, AuAg24(SR)18− and Au2Ag41(SR)26(Dppm)2+ (SR = cyclohexyl mercaptan, Dppm = bis(diphenylphosphino)-methane). The mechanism by which these two nanoclusters coexist is elucidated, and found to entail formation of the unstable AuAg24(SR)18−, followed by its partial conversion to Au2Ag41(SR)26(Dppm)2+ in the presence of di-phosphorus ligands, and an interdependent bi-nanocluster system is established, wherein the two oppositely charged nanoclusters protect each other from decomposition. AuAg24(SR)18 and Au2Ag41(SR)26(Dppm)2 are fully characterized by single crystal X-ray diffraction (SC-XRD) analysis – it is found that their co-crystallization results in single crystals comprising equimolar amounts of each. The findings highlight the interdependent relationship between two individual nanoclusters, which paves the way for new perspectives on nanocluster formation and stability.

Construction of heterometallic clusters with multiple uranium–metal bonds by using dianionic nitrogen–phosphorus ligands

Compared with the prevalent metal–metal bond in transition metals, examples of the actinide–metal bond in heterometallic clusters are rare.

[3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide

The activation of white phosphorus (P4) by transition metal complexes has been studied for decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of unusal diphosphanides from a P5 ligand by treatment with cyanide. New cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent dimine cobalt complex, white phosphorus and diorganochlorophosphanes. Reactions of such complexes with tetraalkylammonium or potassium cyanide afford the first cyclotriphosphido cobaltate anion 5 and rare 1-cyano-diphosphan-1-ide anions [R2PPCN]− (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where cyanide anion coordination to cobalt induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a P atom, releasing the P2 fragment. <br>