M. Angeles García‐Monforte

Homoleptic Organocobalt(III) Compounds with Intermediate Spin

Homoleptic organocobalt(III) compounds with formula [NBu4][Co(III)(C6X5)4] [X = F (3), Cl (4)] were obtained in reasonable yields by chemical oxidation of the corresponding divalent species [NBu4]2[Co(II)(C6X5)4] [X = F (1), Cl (2)]. The [Co(III)(C6X5)4](-)/[Co(II)(C6X5)4](2-) couples are electrochemically related by quasi-reversible, one-electron exchange processes at moderate potential: E1/2 = -0.29 (X = F) and -0.36 V (X = Cl) versus saturated calomel electrode. The [Co(III)(C6X5)4](-) anions in salts 3 and 4 show an unusual square-planar geometry as established by single-crystal X-ray diffraction methods. According to their stereochemistry, these Co(III) derivatives (d(6)) are paramagnetic non-Kramers systems with a large zero-field splitting contribution and no observable electron paramagnetic resonance (EPR) spectrum. The thermal dependence of their magnetic susceptibilities can be explained in terms of a spin-Hamiltonian formalism with S = 1 ground state (intermediate spin) and substantial spin-orbit contribution. The magnetic properties of the square-planar d(7) parent species [NBu4]2[Co(II)(C6X5)4] were also thoroughly studied both at microscopic (EPR) and macroscopic levels (alternating current and direct current magnetization measurements). They behave as S = 1/2 (low spin) systems with mainly (dz(2))(1) electron configuration and a certain degree of s-orbital admixture that has been quantified. The electronic structures of all four open-shell [Co(C6X5)4](q-) compounds (q = 1, 2) accounting for their respective magnetic properties are based on a common orbital energy-level diagram.

New advances in homoleptic organotransition-metal compounds: The case of perhalophenyl ligands

Homoleptic derivatives of formula [M(C(6)X(5))(n)](z-) (X = F, Cl) have been prepared and isolated for every first-row transition metal as well as for several of the heavier ones. The stoichiometry attained in each case (n ranging between 2 and 6) can be understood considering the tendency of a given metal ion to compensate its coordinative and electronic unsaturation, while not incurring severe interligand repulsive effects. The molecular structures associated with each stoichiometry seem, in turn, to be governed by electronic rather than steric factors. Most of these [M(C(6)X(5))(n)](z-) compounds are unsaturated, open-shell organometallic species, not fulfilling the 18-electron (or Effective Atomic Number) rule. This behaviour can be attributed to the absence of pi stabilising ligands (such as CO, phosphines, alkenes, alkynes, a variety of substituted aromatic rings, and so on) which are otherwise ubiquitous in organotransition-metal chemistry. The magnetic properties of the [M(C(6)X(5))(n)](z-) species have been determined by EPR spectroscopy and/or bulk magnetisation measurements. Excellent correlation between molecular geometry and magnetic properties (whether diamagnetic or paramagnetic) has been observed. Many of these compounds undergo chemically- or electrochemically-induced electron exchange processes. These redox reactions proceed without alteration in the stoichiometry of the [M(C(6)X(5))(n)](z-) compound, but usually involve a sharp change in the molecular geometry according to the different electron configuration of the interrelated species.

Unusual luminescent octanuclear stellate platinacycle self-assembled by Pt–Ag bonds

An unprecedented macrocyclic luminescent octanuclear cluster cyclo-[{Pt(C6Cl5)2(mu-OH)(mu-Ag)}4] (Pt-Ag) 2 was self-assembled by the formation of Pt(II)-Ag(I) bonds; the optical properties of this complex were also investigated.

σ-Organoniobium Compounds with [NbR4]− and NbR4 Stoichiometries†

This work was supported by the Spanish MICINN (DGPTC)/FEDER (projects CTQ2008-06669-C02-01/BQU and MAT2008-03461/MAT) and the Gobierno de Aragon (Grupo de Excelencia: Quimica Inorganica y de los Compuestos Organometalicos).

Magnetic Interaction between d1 [MOR4]− Units of Molybdenum and Tungsten

Five-coordinate oxo-derivatives [NBu4][MO(C6F5)4] (1) have been prepared for the heavier Group 6 elements: 1-Mo and 1-W. The magnetic properties of that salts have been studied by a combination of Electron paramagnetic resonance (EPR), calorimetric and magnetochemical techniques, pointing out the existence of weak ferromagnetic interactions. These have been correlated with the arrangement of the magnetic units in the crystal.