A Low-Valent Iron Imido Heterocubane Cluster: Reversible Electron Transfer and Catalysis of Selective C-C Couplings.

Enzymes and cofactors with iron-sulfur heterocubane core structures, [Fe4 S4 ], are often found in nature as electron transfer reagents in fundamental catalytic transformations. An artificial heterocubane with a [Fe4 N4 ] core is reported that can reversibly store up to four electrons at very negative potentials. The neutral [Fe4 N4 ] and the singly reduced low-valent [Fe4 N4 ](-) heterocubanes were isolated and fully characterized. The low-valent species bears one unpaired electron, which is localized predominantly at one iron center in the electronic ground state but fluctuates with increasing temperatures. The electrons stored or released by the [Fe4 N4 ]/[Fe4 N4 ](-) redox couple can be used in reductive or oxidative CC couplings and even allow catalytic one-pot reactions, which show a remarkably enhanced selectivity in the presence of the [Fe4 N4 ] heterocubanes.

Reactivity of an All-Ferrous Iron-Nitrogen Heterocubane under Reductive and Oxidative Conditions.

The reactivity of the all-ferrous FeN heterocubane [Fe4 (Ntrop)4 ] (1) with i) Brønsted acids, ii) σ-donors, iii) σ-donors/π-acceptors, and iv) one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(µ3 -imido) 48 electron complex in the former case and a tetranuclear all ferric µ-oxo-µ-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.

Ambient-Pressure Synthesis of Two New Vanadium-Based Calcium Ferrite-Type Compounds: NaV1.25Ti0.75O4 and NaVSnO4.

Two new CaFe2O4-type compounds NaV1.25Ti0.75O4 (1) and NaVSnO4 (2) have been prepared at ambient pressure and temperatures < 800 °C. This contrasts with the parent material NaV2O4 which is synthesized at 6 GPa and 1300 °C. The lattice parameters are a = 9.1500(4) Å, b = 2.9399(3) Å, and c = 10.6568(5) Å for 1 and a = 9.3083(6) Å, b = 3.0708(2) Å, and c = 10.9194(5) Å for 2 (space group Pnma). Structure refinement against neutron powder diffraction data reveals that V/Ti and V/Sn are disordered over two octahedral sites. Both materials are characterized by a magnetic transition near 150 K below which the Curie moment is reduced from a value consistent with V(3+) [0.75 emu molV(-1) K(-1) for 1 and 0.58 emu molV(-1) K(-1) for 2] to 0.23 emu molV(-1) K(-1) for 1 and 0.30 emu molV(-1) K(-1) for 2, signaling a 70-50% reduction in the paramagnetic moment. The Weiss temperature (θ) is reduced from -285 (1) and -138 K (2) to values close to 0 K, suggesting that the remaining spins are dilute and weakly interacting. Heat capacity measurements reveal a gradual loss of magnetic entropy between 2 and 150 K, consistent with short-range bulk magnetic ordering. In addition, heat capacity and magnetic susceptibility measurements reveal a number of weak magnetic transitions below 6 K involving both antiferromagnetic and ferromagnetic components.

Low-valent iron(i) amido olefin complexes as promotors for dehydrogenation reactions.

Fe(I) compounds including hydrogenases show remarkable properties and reactivities. Several iron(I) complexes have been established in stoichiometric reactions as model compounds for N2 or CO2 activation. The development of well-defined iron(I) complexes for catalytic transformations remains a challenge. The few examples include cross-coupling reactions, hydrogenations of terminal olefins, and azide functionalizations. Here the syntheses and properties of bimetallic complexes [MFe(I) (trop2 dae)(solv)] (M=Na, solv=3 thf; M=Li, solv=2 Et2 O; trop=5H-dibenzo[a,d]cyclo-hepten-5-yl, dae=(N-CH2 -CH2 -N) with a d(7) Fe low-spin valence-electron configuration are reported. Both compounds promote the dehydrogenation of N,N-dimethylaminoborane, and the former is a precatalyst for the dehydrogenative alcoholysis of silanes. No indications for heterogeneous catalyses were found. High activities and complete conversions were observed particularly with [NaFe(I) (trop2 dae)(thf)3 ].

Large enhancement of the thermopower in Na(x)CoO2 at high Na doping.

Research on the oxide perovskites has uncovered electronic properties that are strikingly enhanced compared with those in conventional metals. Examples are the high critical temperatures of the cuprate superconductors and the colossal magnetoresistance in the manganites. The conducting layered cobaltate Na(x)CoO2 exhibits several interesting electronic phases as the Na content x is varied, including water-induced superconductivity and an insulating state that is destroyed by field. Initial measurements showed that, in the as-grown composition, Na(x)CoO2 has moderately large thermopower S and conductivity sigma. However, the prospects for thermoelectric cooling applications faded when the figure of merit Z was found to be small at this composition (0.60.75, S undergoes an even steeper enhancement. At the critical doping x(p) approximately 0.85, Z (at 80 K) reaches values approximately 40 times larger than in the as-grown crystals. We discuss prospects for low-temperature thermoelectric applications.

Formation of metal-anion arrays within layered perovskite hosts. Preparation of a series of new metastable transition-metal oxyhalides, (MCl)LaNb(2)O(7) (M = Cr, Mn, Fe, Co).

A new series of transition-metal oxyhalides (MCl)LaNb(2)O(7) (M = Cr, Mn, Fe, Co) have been prepared by a simple topochemical route. Layered perovskite hosts (ALaNb(2)O(7), A = Li, Na, K or Rb) were reacted with the corresponding anhydrous metal halides under mild reaction conditions (<400 degrees C). The compounds were examined by X-ray powder diffraction; the series appears to be isostructural with (CuCl)LaNb(2)O(7), and the layer spacings, with the exception of M = Co, follow the trend expected from transition-metal cationic radii. Thermal analysis with differential scanning calorimetry (DSC) shows the materials to be metastable where all four compounds decompose exothermically above 690 degrees C.