Redox Pairs of Diiron and Iron-Cobalt Complexes with High-Spin Ground States.

A series of iron and iron-cobalt bimetallic complexes were isolated: LFeCl (1), LFe (2), Li(THF)[LFeCl](Li(THF)[2-Cl]), LFeCoCl (3), and LFeCo (4), where L is a trianionic tris(phosphineamido)amine ligand. As elucidated by single-crystal X-ray diffraction studies and quantum-chemical calculations, the FeFe and FeCo complexes, 1 and 3, respectively, have weak metal-metal interactions (the metal-metal distances are 2.63 and 2.

Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel.

The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consistently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favourable in others.

Encapsulating zinc(II) within a hydrophobic cavity.

A new macrobicyclic ligand has been prepared, and it is shown to bind Zn(2+) on the inside. The ligand consists of a triamido(amine) motif to coordinate the metal ion and a narrow, hydrophobic channel above the metal binding site.

Study of the conformationally flexible, wide bite-angle diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran in rhodium(I) and palladium(II) coordination complexes.

The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as (iPr)DPDBFphos) was prepared and studied for its potential as a trans-chelating ligand in transition-metal coordination complexes. In the rhodium norbornadiene complex [((iPr)DPDBFphos)Rh(NBD)]BF(4), which has been characterized with multinuclear NMR spectroscopy, X-ray crystallography, and electrochemical studies, the ligand binds in cis fashion. In the bis(acetonitrile) complexes of rhodium and palladium [((iPr)DPDBFphos)M(CH(3)CN)(2)](BF(4))(n) (M = Rh, Pd; n = 1, 2), the ligand adopts a trans coordination geometry.