Reaction of activated palladium metal with a HNO3/acetic acid mixture produces both orange Pd3(OAc)6, 1, and purple Pd3(OAc)5(NO2), 2. Compound has a trinuclear structure derived from that of the well-known triangular complex 1 in which one acetate group has been replaced by a nitrite group which is bonded to one palladium atom by the nitrogen atom and to another Pd atom using one of the oxygen atoms. Highly pure 1 can be made by continuous removal of the nitric oxides from the reaction mixture using a flow of N2. 1H NMR spectra of solutions of 1 in CDCl3 and C6D6 show several signals of various intensities when a small amount of water is present in the deuterated solvents but only one signal when the solvents are thoroughly dried. These results are consistent with the occurrence of one or more hydrolysis processes when the solvents contain water and suggest that hypotheses about various [Pd(OAc)2]n aggregates that have previously been brought forward in the literature to explain the complexity of the spectrum of 1 are unnecessary, especially for nonpolar solvents. Compound 2 does not hydrolyze, and in wet or dried solvents shows a 1H NMR spectrum that consists of five equal-intensity signals due to the five nonequivalent acetate groups.

Two synthetic routes-ion-exchange preparation from layered Na(3)Ni(2)SbO(6) at 300 °C and direct solid-state synthesis at 1150 °C resulted in layered Li(3)Ni(2)SbO(6), a cation-ordered derivative from the rocksalt type. The Fddd form reported earlier could not be reproduced. According to the XRD Rietveld analysis, Li(3)Ni(2)SbO(6) is a pseudohexagonal monoclinic structure, C2/m, with a = 5.1828(2) Å, b = 8.9677(3) Å, c = 5.1577(2) Å, β = 109.696(2)°. No Li/Ni mixed occupancy was detected. At high temperatures, the magnetic susceptibility follows the Curie-Weiss law with a positive value of Weiss temperature, ∼8 K, indicating a predominance of ferromagnetic interactions. However, Li(3)Ni(2)SbO(6) orders antiferromagnetically at T(N)∼ 15 K. The effective magnetic moment is 4.3 μ(B)/f.u. which satisfactorily agrees with theoretical estimations assuming high-spin configuration of Ni(2+) (S = 1). Electron spin resonance (ESR) spectra show single Lorentzian shape line attributed to Ni(2+) ion in octahedral coordination. The absorption is characterized by isotropic temperature independent effective g-factor g = 2.150 ± 0.005. In accordance with the layered honeycomb crystal structure determined for Li(3)Ni(2)SbO(6), the superexchange interaction between Ni(2+) ions through Ni-O-Ni pathways within Ni(2)SbO(6) layers are assumed to be ferromagnetic, while the dominant interaction between layers is antiferromagnetic.

Structure, electrochemical, magnetic and resonance properties of new layered antimonate Li(4)FeSbO(6) were comprehensively studied using powder X-ray diffraction, cyclic voltammetry, magnetic susceptibility, heat capacity, electron spin resonance and Mössbauer spectroscopy. In the crystal structure the iron ions form the triangular network within (LiFeSbO(6))(3-) layers alternating with nonmagnetic lithium layers. The electrochemical activity studied implies an Fe(3+)/Fe(4+) redox couple at 4.3 V (ox.) and 3.9 V (red.) thereby revealing that Li can be reversibly extracted. The long-range antiferromagnetic order was found to occur at the Néel temperature, T(N) ≈ 3.6 K, confirmed both by the magnetic susceptibility data and specific heat ones. The effective magnetic moment is estimated to be 5.93 μ(B)/f.u. and satisfactorily agrees with theoretical estimations assuming high-spin configuration of Fe(3+) (S = 5/2). In the magnetically ordered state, though, the magnetization demonstrates rather peculiar behavior. An additional anomaly on the M(T) curves appears at T(2) < T(N) in moderate magnetic field. The positions of transitions at T(N) and T(2) separate increasingly with increasing external field. Multiple measurements consistently demonstrated field-sensitive moving of magnetic phase boundaries constituting a unique phase diagram for the compound under study. The complex low-dimensional (2D) nature of magnetic coupling was confirmed by the dynamic magnetic properties study. Electron spin resonance from Fe(3+) ions in paramagnetic phase is characterized by a temperature independent effective g-factor of 1.99 ± 0.01. However, the distortion and broadening of the ESR line were found to take place upon approaching the magnetically ordered state from above. The divergence of the temperature-dependent linewidth is analyzed in terms of both critical behavior close to long-range magnetic order and the Berezinskii-Kosterlitz-Thouless (BKT)-type transition. Heat capacity measurements even at zero field manifested an appearance of the additional anomaly at temperatures below the Néel temperature. The temperature dependence of ESR intensity, linewidth and shift of the resonant field imply an extended region of short-range order correlations in the compound studied. The rich variety of the anomalies in magnetic and resonance properties makes this new antimonate a very interesting system to investigate the multiple phase transitions and competing exchange interaction due to the critical role of the layered structure organization accompanied by the frustration effects in triangular antiferromagnets.

Dinickel(II) complexes of the ligands N,N'-di-p-anisylformamidinate (DAniF) and N,N',N''-triphenylguanidinate (TPG) have been synthesized and crystallographically characterized, along with their one-electron-oxidized analogues. In both systems, the Ni-Ni distances become shorter by approximately 0.1 A upon oxidation, in accord with the proposal that the resulting Ni2(5+) complexes are appropriately described as having one electron removed from a metal-based sigma orbital and an overall Ni-Ni bond order of 1/2. Although conventional DFT calculations on the model compounds Ni2(HNCHNH)4 and [Ni2(HNCHNH)4]+ appear to predict that the lowest energy state of the latter species would have one unpaired electron in an essentially ligand-based orbital. A single-point calculation of Ni2(DAniF)4 employing the geometry of its crystal structure with the full ligand included reveals a reversal of the previously predicted order of the HOMO and HOMO-1, and suggests that the unpaired electron in [Ni2(DAniF)4]+ is in a metal-based orbital of sigma symmetry. This is verified by the axial EPR spectrum of the compound in solution. The compound Ni2(DAniF)4 shows an unexpectedly rich cyclic voltammogram with four stepwise reversible oxidation waves. Coulometric experiments show that the doubly oxidized species has a significant lifetime at -25 degrees C, and by spectroelectrochemistry, its UV-vis spectrum was recorded. We propose that this species contains a Ni2(6+) core with a single Ni-Ni sigma bond.