Search results for "HSAB theory"
showing 5 items of 5 documents
Orbital-controlled reactions catalysed by zeolites: Electrophilic alkylation of aromatics
1994
The role of orbital control in product selectivity during electrophilic aromatic alkylation catalysed by zeolites was studied both theoretically and experimentally. In order to discuss this, the alkylation of toluene and m-xylene by methanol was carried out on a series of large-pore zeolites (HY). The changes in the para to ortho ratio observed on changing the framework Si/Al ratio of the zeolites were related to ab initio molecular orbital calculations of the LUMO energy of structurally alike model clusters but containing different tetrahedral cations around the active site. The observed correlation is discussed in terms of the HSAB principle by taking into account the influence of the cat…
Effect of anion substitution on the structural and transport properties of argyrodites Cu7PSe6−xSx
2019
Inspired by the good performance of argyrodites as ion conducting thermoelectrics and as solid electrolytes we investigated the effect of isovalent S2- substitution for Se2- in Cu7PSe6. At room temperature Cu7PSe6 crystallizes in the primitive cubic β-polymorph of the argyrodite structure and transforms to the face-centered high-temperature (HT) γ-modification above 320 K. The transition for the homologous Cu7PS6 occurs at 510 K. Promising thermoelectric and ion conducting properties are observed only in the HT modification, where the cations are mobile. Using Rietveld refinements against X-ray diffraction data the effect of isovalent S2- substitution for Se2- on the structural and transpor…
Investigations on organoantimony compounds XI. Triorganoantimony(V) compounds containing potentially tridentate ligands
1974
Triorganoantimony(V) compounds of the types RSbVL, in which R = Me or Ph, and L represents a potentially tridentate dianionic Schiff base ligand of the ONO or SNO type, have been synthesized and investigated by spectroscopic (UV, IR, PMR) methods. Molecular weight determinations in benzene reveal the monomeric nature of these compounds. The free ligands, HL, used in this study are:,′-(methylidynenitrilo)diphenol (HSab), -(o-hydroxyphenyl)benzothiazoline (H-Sat), -(o_hydroxyanilino)crotonophenone (HBah), 4-(o-hydroxyphenylimino)--pentanone (HAah) and -acetonyl--methylbenzothiazoline (HAat). Both the UV and the IR data suggest hexacoordinate molecular structures for the complexes RSbL in whic…
Reactivity of 4,4-Dichloro-1,1-diphenyl-2-azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π-Conjugated 2-Azabutadienes and …
2006
Treatment of 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2C=C(H)-N=CPh2] (1) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2-azabutadiene derivatives (RS)2C=C(H)–N=CPh2 (2) (2a R = iPr; 2b R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on 1 afforded as the sole product the six-membered heterocyclic compound ethyl 2-ethoxycarbonylmethylthio-5,5-diphenyl-5,6-dihydro-4H-1,4-thiazine-6-carboxylate (5). The reaction is initiated by substitution of the two vinyl-bound chloro substituents to give {EtO(O=)CCH2S}2C=C(H)–N=CPh2 (2c) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2-azabu…
From Single Molecules to Nanoscopically Structured Materials: Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on the Degree of P…
2011
A chemically specific and facile method for the immobilization of metal oxide nanoparticles onto the surface of IF-MoS2 nested fullerenes is reported. The modification strategy is based on the chalcophilic affinity of transition metals such as Fe2+/Fe3+, Fe3+, or Zn2+ as described by the Pearson HSAB concept. The binding capabilities of the 3d metals are dictated by their Pearson hardness. Pearson hard cations such as Fe3+ (Fe2O3) do not bind to the chalcogenide surfaces; borderline metals such as Fe2+ (Fe3O4) or Zn2+ (ZnO) bind reversibly. Pearson-soft metals like Au bind irreversibly. The immobilization of metal oxide nanoparticle colloids was monitored by transmission electron microscopy…