Synthesis and reactivity of water-soluble platinum(II) complexes containing nitrogen ligands

A series of water-soluble platinum(II) complexes containing bidentate imino pyridine ligands L of the general formula LPtX₂ (X=Cl or Me) have been prepared. The dichloro complexes are very stable in water or dimethyl sulfoxide (DMSO), even at elevated temperatures, whereas the dimethyl complexes are less stable in these strongly polar solvents. In DMSO, an equilibrium between the complex LPtMe₂ and (DMSO)₂PtMe₂ is observed, whereas in water decomposition is observed within 1 day at room temperature.     

On the role of anion templates for the self-assembly of octanuclear copper(I) dichalcogenophosph(in)ate clusters

The octanuclear Cu^I cubic clusters [Cu₈(S₂PPh₂)₆]²⁺ (1) and [Cu₈(μ₈-Cl)(S₂PPh₂)₆]⁺ (2) have been prepared and crystallographically characterized, and their cluster bonding modes investigated with density functional theory (DFT) calculations. Both are rare examples of metal dithiophosphinate clusters and 1 is the first example of a non anion-centered or ‘empty’ dithiophosph(in)ate Cu^I₈ cube. DFT calculations indicate that the stability of the empty cluster 1 can be attributed to its strong metal–ligand interactions, with no significant Cu?Cu bonding interactions present. Comparison of the solid-state structures of 1, 2 and the analogous sulfide centered cluster [Cu₈(μ₈-S)(S₂PPh₂)₆] (3) reveals a significant contraction of the octanuclear Cu^I₈ cube upon anion encapsulation. This contraction is shown, using DFT calculations, to be predominately assignable to the ionic interaction between the Cu^I cations and the encapsulated anion center.