Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters

The reaction of [CuI(HSC₆H₄PPh₂)]₂ with NaBH₄ in CH₂Cl₂/EtOH led to air‐ and moisture‐stable copper hydride nanoparticles (CuNPs) containing phosphinothiolates as new ligands, one of which was isolated by crystallization. The X‐ray crystal structure of [Cu₁₈H₇L₁₀I] (L=^?S(C₆H₄)PPh₂) shows unprecedented features in its 28‐atom framework (18 Cu and 10 S atoms). Seven hydrogen atoms, in hydride form, are needed for charge balance and were located by density functional theory methods. H₂ was released from the copper hydride nanoparticles by thermolysis and visible light irradiation.     

Cover Picture: Chem. Eur. J. 2/2003

The cover picture conveys the concise message that a fixed element of axial chirality residing in one ring of a catenane can induce chirality of a helical nature within a dynamic setting in the other (interlocked) ring. The overwhelming preference for one enantiomeric pair within a bipartite set of diastereoisomers relating to the particular [2]catenane, presented as its X‐ray crystal structure in the circular inset, becomes more and more pronounced as its 1,4‐dioxybenzene units are replaced, one at a time, by 1,5‐dioxynaphthalene ones, with their concomitant planar chiralities. The very high levels of induction of dynamic helical and planar chiralities by a fixed source of axial chirality in a simple catenane conjures up a number of scenarios where this approximately cubic nanometer of programmable information might be put to good use. For more details concerning these tiny stereochemical wonders with no stereogenic center in sight, see the article on p. 543 ff by J. F. Stoddart and D. J. Williams and the wizards that work their magic for them.