Linking [Fe(III)3] triangles with "double-headed"phenolic oximes

The use of "double-headed" phenolic oximes produces a trigonal antiprismatic [Fe(III)(3)](2) cluster with an "internal cavity" filled with an additional Fe(3+) ion. Magnetic measurements reveal that the competition between different exchange interactions leads to a low-spin ground multiplet weakly separated in energy from a complex pattern of low-lying excited levels.     

Energy partitioning in photodissociation and photosensitization

The molecular dynamics of photodissociation and of electronic vibrational/translational energy transfer have been investigated in terms of an impulsive ‘half-collision’ model, modified to accommodate the possibility of changes in the potential energy functions (force constants) of the separating fragments. The model, which is suitable for any system which is suddenly prepared on a repulsive potential energy surface (e.g. following electronic excitation or radiationless transition), has been applied to the quenching of Hg(6³P₁) by CO and NO and to the photodissociation of ICN. Experimental data and alternative theoretical treatments are available for each of these systems. The new model is able to achieve a remarkable agreement with observation in the Hg/CO and NO systems by assuming the intermediate formation of a Hg(6³P₀) - CO or NO complex in which the C-O or N-O bond order increases by ～ 0·6. Model calculations for the quenching of Cd and Zn(³P₀) suggest that the distributions over final states would be very similar to that for Hg(³P₀).

A re-appraisal of the near U.V. photo-dissociation of ICN indicates that CN radicals should be formed preferentially in the òπ electronic state; those observed in the ground state should be vibrationally excited whether they appear as primary photo-products or not.

In general, changes in the equilibrium bond length of the molecular fragment as the system transfers onto the repulsive potential surface, are crucial in determining both the level of vibrational excitation and the detailed distribution over final states. When the molecular fragment has a large force constant the ‘steepness’ of the potential surface is relatively unimportant.     

Crystal and molecular structure of di(perchlorato)(1,4,8,11-tetraazacyclotetradecane)copper (II). Cu(cyclam) (ClO4)2

The title compound, Cu(C₁₀H₂₄N₄)(ClO₄)₂, crystallizes in the triclinic system with unit cell dimensionsa= 8.744,b= 8.022,c= 8.677 Å, α = 118.7, β = 56.9, γ = 113.5 °,Z= 1, space group P¯1. The structure was solved by Fourier methods and refined by least-squares techniques using the 1545 nonzero three-dimensional counter-diffraction intensity data (CuKα) to give a conventionalR factor of 0.056. The coordination sphere of the copper ion is defined by a planar arrangement of the four nitrogen donors in the macrocyclic ligand with oxygen atoms from the perchlorate groups lying above and below this plane. The resulting tetragonally distorted octahedron of donor atoms gives interatomic distances Cu?N = 2.02(4) Å and 2.02(3) Å, and Cu?N = 2.57(4) Å.     

Surface binding vs. sequestration; the uptake of benzohydroxamic acid at iron(iii) oxide surfaces

Benzohydroxamic acid is shown to be an unexpectedly good ligand for iron(iii) oxides, favouring surface attachment to the formation of trisbenzohydroxamato complexes, which are known to have very high thermodynamic stability in solution.     

A Simple Primary Amide for the Selective Recovery of Gold from Secondary Resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl₄]^? ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. The fundamental chemical understanding gained herein should be integral to the development of metal‐recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.     

Anion selectivity in zwitterionic amide-functionalised metal salt extractants

Amide-functionalised salen ligands capable of extracting metal salts have been synthesised and characterised. Single-crystal X-ray structure determinations of complexes of NiSO4, [Ni(L)(SO4)], confirm that the ionophores are in a zwitterionic form with Ni(II) bound in the deprotonated salen moiety and the SO4(2-) ion associated with protonated pendant N'-amidopiperazine groups. Treatment of [Ni(L)(SO4)] with base removes the protons from the pendant amido-amine group resulting in loss of the SO4(2-) ion and formation of metal-only complexes of type [Ni(L-2H)], which have been characterized by single-crystal X-ray diffraction. Three of the ligands with solubilities suitable for solvent extraction studies show loading and stripping pH-profiles that are suitable for the recovery of CuSO4 or CuCl2 from industrial leach solutions. The copper-only complexes, [Cu(L-2H)], are selective for Cl- over SO4(2-) in both solvent extraction and bulk liquid membrane transport experiments and were found to bind Cl- in two steps via the formation of a 1:1:1 [Cu(L-H)Cl] assembly, followed by a 1:1:2 [Cu(L)Cl2] assembly as the pH of the aqueous phase is lowered. The anion transport selectivity was evaluated for a number of other mono-charged anions and interestingly the ligands were found to display a preference for the Br- ion. To probe the influence of the Hofmeister bias on the selectivity of anion complexation, single-phase potentiometric titration experiments were employed to investigate the binding of SO4(2-) and Cl- by one of the copper only complexes, [Cu(L-2H)] in 95 %/5 % MeOH/water. Under these conditions selectivity was reversed (SO4(2-)>Cl-) confirming that the Hofmeister bias, which reflects the relative hydration energies of the anions, dominates the selectivity of anion extraction from aqueous media into CHCl3.