The synthesis and structural characterisation of three small nickel(II) cages are reported, all stabilised by pivalate ligands. The magnetic properties of the cages have been studied by a combination of susceptibility measurements and inelastic neutron scattering. For a dinuclear cage, [Ni2(mu-OH2)(O2CCMe3)4(HO2CCMe3)4] 1 the ground state is S=2, with a ferromagnetic exchange interaction betwee...

Dicationic tetranuclear ruthenium octahydride [(Cp*Ru)4H8]2+ (5) with tetrahedral geometry was obtained by reaction of dinuclear ruthenium tetrahydride (Cp*Ru)2(μ-H)4 (1) with an excess of Brønsted acids, such as HBF4·OEt2, in toluene. Monocationic tetraruthenium heptahydride [(Cp*Ru)4H7]+ (7) was obtained by dropwise addition of a diluted acid to a rigorously stirred solution of 1 at ambient t...

Six new pentamethylcyclopentadienyl Rh(III) and Ir(III) metalla-rectangles ([3](CF3SO3)4-[8](CF3SO3)4) have been prepared by a self-assembly strategy using the embelin-derived metalla-clips (η5-C5Me5)2M2(μ4-C6HRO4-κO)Cl2 (M = Rh, 1; M = Ir, 2; R = (CH2)10CH3) and the linear ditopic ligands, pyrazine, 4,4'-bipyridine and 1,2-bis (4-pyridyl)ethylene. These new metalla-rectangles have been obtaine...

Reactions of unbridged zirconocene dichlorides, (R(n)C(5)H(5-n))(2)ZrCl(2) (n = 0, 1, or 2), with diisobutylaluminum hydride (HAl(i)Bu(2)) result in the formation of tetranuclear trihydride clusters of the type (R(n)C(5)H(5-n))(2)Zr(mu-H)(3)(Al(i)Bu(2))(3)(mu-Cl)(2), which contain three [Al(i)Bu(2)] units. Ring-bridged ansa-zirconocene dichlorides, Me(2)E(R(n)C(5)H(4-n))(2)ZrCl(2) with E = C or...

With the goal to study the mechanisms of dinuclear metalloenzymes, new synthetic and computational models for such proteins were prepared and studied. Multidentate ligands based on a central phenolate and with imidazoleand carboxylate-containing donor moieties were synthesized to simulate carboxylate-rich ligand environments. The two ligands that were found to be the most useful, were the symme...

The development of methodologies to control on demand and reversibly supramolecular transformations from self-assembled metalla-structures requires the rational design architectures able answer an applied stimulus. While solvent or concentration changes, light exposure addition a chemical have been largely explored provide these transformations, case pH sensitive materials is less described. He...