NMR parameters of the tetrahedrane [Fe2(CO)6(μ-SNH)], studied by experiment and DFT

The intramolecular dynamic behavior of the tetrahedrane-type cluster [Fe₂(CO)₆(μ-SNH)] 1 was studied by ¹³C NMR spectroscopy. The ⁵⁷Fe chemical shift of 1 and the coupling constants ¹ J(⁵⁷Fe,¹³C) were measured. These NMR parameters, and also ¹ J(⁵⁷Fe,¹⁵N), were found to be in good agreement with data calculated by using density functional theory (DFT) methods (B3LYP), based on the geometry calculated at the 6-311+G(d,p) level of theory. The isolobal replacement of the Fe(CO)₃ with BH fragments leads to the tetrahedranes [Fe(CO)₃(BH)(μ-SNH)] 2 and [(HB)₂(μ-SNH)] 3. Both were identified by calculations as minima on the respective potential energy surface (PES). However, the tetrahedrane-type structure of 3 is much higher in energy when compared with the planar cyclic isomers 3a and 3b.     

Fe(Cp)2PF6: An efficient catalyst for cyanosilylation of carbonyl compounds under solvent free condition

An efficient method for the addition of trimethylsilyl cyanide (TMSCN) to various aldehydes and ketones has been described using Fe(Cp)₂PF₆ (2.5 mol%) as a catalyst under solvent free condition. Excellent yields of trimethylsilylether of cyanohydrin up to (94%) was achieved within 10 min.     

不同光滑度立方体氧化铁对液晶电光性能的改善

向列相液晶被广泛应用于液晶显示中,但是由于杂质的存在,会导致液晶的驱动电压变大,增加能耗。 为了降低阈值电压和饱和电压,通常向液晶中添加纳米颗粒来提高电光性能。 本文利用水热法制备了表面粗糙和光滑的两种立方体Fe₂O₃纳米颗粒,其形貌均匀,尺寸约550 nm。 将二者分别掺杂到向列相液晶E7中,结果表明,粗糙立方体Fe₂O₃/E7复合体系具有比光滑立方体Fe₂O₃/E7复合体系和向列相液晶E7更优的电光性能,且在掺杂质量分数为0.4%时,其电光性能达到最优,阈值电压和饱和电压分别降低9.9%和11.6%,对比度增大80%,响应时间降低至6.0 ms。 这归因于粗糙立方体Fe₂O₃具有足够的表面积和表面所带电荷更多,所以会更易吸附体系中的杂质离子和减弱杂质离子的屏蔽作用,从而提高了电光性能。     

The crystal structure of Fe(SeO2OH)(SeO4)·H2O

Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO₂OH) (SeO₄) · H₂O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, space group P2₁/c,R=0.029,R _w=0.027 for 2430 independent reflections (sin /0.76 Å^–1). Isolated FeO₅(H₂O)-octahedra share five corners with [SeO₂OH] and [SeO₄] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.

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Die Kristallstruktur von Fe(SeO₂OH)(SeO₄)·H₂O

Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO₂OH) (SeO₄)·H₂O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, Raumgruppe P2₁/c,R=0.029,R _w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å^–1). Isolierte FeO₅(H₂O)-Oktaeder teilen fünf Ecken mit [SeO₂OH]- und [SeO₄]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.

     

Survey of ligand field parameters of strong field d complexes obtained from the g matrix

Using a newly proposed approach involving an internally consistent set of equations, the ligand field parameters Δ/ξ, V/ξ and k are obtained from literature values of the g matrix for strong field d⁵ systems of various conformations in which |Δ/ξ|≤10. Qualitative analysis of the observed results is done using the Angular Overlap Model, AOM.     

Comparative evaluation of Fe(III) reducing power-based antioxidant capacity assays in the presence of phenanthroline, batho-phenanthroline, tripyridyltriazine (FRAP), and ferricyanide reagents

The chemical diversity of antioxidants in complex matrices such as plant extracts makes it difficult to separate and quantify antioxidants from these solutions. Therefore it is desirable to establish methods that can measure the total antioxidant capacity (TAC) levels directly from plant extracts. Iron(III)-based TAC assays, especially the most widely used FRAP (ferric-reducing antioxidant power), play an important role in this regard. However, many problems have been reported in the application of the FRAP assay, the most serious one being the incomplete oxidation of a number of antioxidants during the time protocol of the assay. Thus, six different ferric ion-based total antioxidant capacity (TAC) assays have been comparatively tested, modified, and improved so as to obtain more sensitive and precise results for complex mixtures, namely: 1,10-phenanthroline (o-phen) method (with incubation), batho-phenanthroline method (with incubation), original FRAP method, modified FRAP method (with incubation), original ferricyanide method, and modified ferricyanide method (with incubation). Two new assays in this regard (i.e., o-phen and batho-phen) have been established, and the existing assays (FRAP and ferricyanide) have been modified so as to let the oxidation reactions of antioxidants reach completion. The molar absorptivity for a variety of antioxidants was highest for modified FRAP, batho-phen, and original FRAP methods. The absorption maximum wavelength shifted batochromically to a higher extent for modified ferricyanide, FRAP, and batho-phen procedures, decreasing the possibility of interferences due to organics absorbing in the near-UV range of the visible spectrum where most antioxidant assays are performed. The linear concentration ranges were shown to be further extended and linear correlation coefficients improved with respect to the most widely used ferric-based assay, FRAP. Of the six assays tested and developed, only the modified ferricyanide procedure gave high intercept values and low addivitity of TAC values of constituents in complex mixtures, requiring further attention of method optimization. Thus, it was shown that the most widely used FRAP could be effectively modified, and o-phen, batho-phen, and ferricyanide methods constitute cheaper alternatives to FRAP under certain conditions, with partly improved molar absorptivity (and thus sensitivity) for antioxidants, lower intercept values (and higher precision), broader linear range (and higher flexibility), and better additivity of TAC values of antioxidant constituents in mixtures.     

M?ssbauer and other spectral studies of Fe(III) complexes of benzothiazolines

Different molar reactions of Fe(OPr¹)₃, and FeCl₃ with benzothiazolines having an NSH donor system. derived by the condensation ofo-aminothiophenol with heterocyclic aldehydes. viz. pyridine-2-aldehyde. furfuraldehyde and thiophene-2-aldehyde. lead to the formation of [Fe.Pr¹(NS)₂]₂, [Fc(NS)₃] and [Fe(NS)₂Cl| type of complexes. The resulting derivatives have been characterized by elemental analysis, conductivity measurements, molecular weight determinations and magnetic studies. IR, electronic, M?ssbauer and ESR spectral data have been used to deduce the structures of the resulting derivatives.     

Effect of ionic interactions on the oxidation of Fe(II) with H2O2 in aqueous solutions

The oxidation of Fe(II) with H₂O₂ has been measured in NaCl and NaClO₄ solutions as a function of pH, temperature T (K) and ionic strength (M, mol-L^–1). The rate constants, k (M^–1-sec^–1), d[Fe(II)]/DT=-k[Fe(II)][₂O₂]at pH=6.5 have been fitted to equations of the formlog k = log k₀+ AI ^1/2+BI+CI ^1/2/T Where log k₀=15.53-3425/T in water; A=–2.3, –1.35; B=0.334, 0.180; and C=391, 235, respectively, for NaCl (=0.09) and NaClO₄ ( =0.08). Measurements made in NaCl solutions with added anions yield rates in the order B(OH) ₄ ^– >HCO ₃ ^– >ClO ₄ ^– >Cl^–>NO ₃ ^– >SO ₄ ^2– and are attributed to the relative strength of the interactions of Fe²⁺ or FeOH⁺ with these anions. The FeB(OH) ₄ ⁺ species is more reactive while the FeCO ₃ ⁰ , FeCl⁺, FeNO ₃ ⁺ and FeSO ₄ ⁰ species are less reactive than the FeOH⁺ ion pair. The general trend is similar to our earlier studies of the oxidation of Fe(II) with O₂ except for B(OH) ₄ ^– . The effect of pH on the logk was found to be a quadratic function of the concentration of H⁺ or OH^– from pH=4 to 8. These results have been attributed to the different rate constants for Fe²⁺ (k₀) and FeOH⁺ (k₁) which are related to the measured k by, k=k_0Fe + k_1FeOH, where _i is the molar fraction of species i. The rates increase due to the greater reactivity of FeOH⁺ compared to Fe²⁺. k₀ is independent of composition and ionic strength but k₁ is a function of ionic strength and composition due to the interactions of FeOH⁺ with various anions.