A new powerful and oxidatively rugged pyrazolate-based water oxidation catalyst of formula {[Ru(II)(py-SO3)2(H2O)]2(μ-Mebbp)}(-), 1(H2O)2(-), has been prepared and thoroughly characterized spectroscopically and electrochemically. This new catalyst has been conceived based on a specific ligand tailoring design, so that its performance has been systematically improved. It was also demonstrated how subtle ligand modifications cause a change in the O-O bond formation mechanism, thus revealing the close activation energy barriers associated with each pathway.
The new pyrazolate-bridged proligand 4-methyl-3,5-bis{6-(2,2'-bipyridyl)}pyrazole ((Me)LH) has been synthesized. Similar to its congener that lacks the backbone methyl substituent ((H)LH) it forms a robust Fe(II)4 grid complex, [(Me)L4Fe(II)4](BF4)4. The molecular structure of [(Me)L4Fe(II)4](BF4)4·2MeCN has been elucidated by X-ray diffraction, revealing two high-spin (HS) and two low-spin (LS) ferrous ions at opposite corners of the rhombic metal ion arrangement. SQUID and (57)Fe Mössbauer data for solid material showed that this [HS-LS-HS-LS] configuration persists over a wide temperature range, between 7 and 250 K, while spin-crossover sets in only above 250 K. According to Mössbauer spectroscopy a [1HS-3LS] configuration is present in solution at 80 K. Thus, the methyl substituent in [(Me)L](-) leads to a stronger ligand field compared to parent [(H)L](-) and hence to a higher LS fraction both in the solid state and in solution. Cyclic voltammetry of [(Me)L4Fe(II)4](BF4)4 reveals four sequential oxidations coming in two pairs with pronounced stability of the di-mixed-valence species [(Me)L4Fe(II)2Fe(III)2](6+) (K(C) = 3.35 × 10(8)). The particular [HS-LS-HS-LS] configuration as well as the di-mixed-valence configuration, both with identical spin or redox states at diagonally opposed vertices of the grid, make this system attractive as a molecular component for quantum cellular automata.
The description of the foot of the wave analysis (FOWA) applied to the electrocatalytic oxidation of water to dioxygen is reported for cases where the rate determining step is first order and second order with regard to catalyst concentration. This coincides with the so called water nucleophilic attack (WNA) and interaction of two M-O units (I2M) mechanism respectively. The newly adapted equations are applied to a range of relevant molecular catalysts both in homogeneous and heterogeneous phase and the kinetic parameters, including apparent rate constants and turnover frequencies, are determined. In this respect the application of FOWA at different catalyst concentrations allows elucidating the reaction mechanism that operates in each case. In addition catalytic Tafel plots are used for assessing the performance of several molecular water oxidation catalysts (WOCs) as a function of overpotential under analogous conditions and thus can be used for benchmarking purposes. While this had been earlier carried out for oxide based WOCs, now it is the first time reported for molecular WOCs.
A disiladicarbene, (Cy-cAAC)2Si2 (2), was synthesized by reduction of Cy-cAAC:SiCl4 adduct with KC8. The dark-colored compound 2 is stable at room temperature for a year under an inert atmosphere. Moreover, it is stable up to 190 °C and also can be characterized by electron ionization mass spectrometry. Theoretical and Raman studies reveal the existence of a Si═Si double bond with a partial double bond between each carbene carbon atom and silicon atom. Cyclic voltammetry suggests that 2 can quasi-reversibly accept an electron to produce a very reactive radical anion, 2(•-), as an intermediate species. Thus, reduction of 2 with potassium metal at room temperature led to the isolation of an isomeric neutral rearranged product and an anionic dimer of a potassium salt via the formation of 2(•-).
Solution-based trimethylaluminum treatment of NCM811 cathode material leads to drying and coating in a single step and therefore improved cycling performance.
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