Electrochemical behaviour of molybdenum-nitrosyl complexes of the type Mo(NO)2Cl2L2 and Mo(NO)Cl3L2

1982 ◽  
Vol 47 (6) ◽  
pp. 1721-1732 ◽  
Author(s):  
Jiří Mašek ◽  
Jan Fiedler ◽  
Jiří Klíma ◽  
Karl Seyferth ◽  
Rudolph Taube

Electrochemical behaviour of 22 molybdenum-nitrosyl complexes of the title types serving as catalyst precursors of olefin metathesis reactions was investigated and the odd-electron localization in the 1-electron reduction products was determined by ESR spectroscopy. It was found that the mononitrosyl complexes containing the fragment {Mo(NO)}4 are reduced in a potential region more positive and distinctly separated from that of the dinitrosyl complexes containing the fragment {Mo(NO)2}6. In the reduction of the former complexes the electrons are accepted into a MO having prevailingly metal d-character while with the latter class of complexes the electrons accepted in the reduction are accommodated in a π-NO based MO. The comparison of the electrochemical results with the catalytic activity of the corresponding systems shows that the ability of the precursor complexes to form the catalytically active species depends on their substitution lability rather than on their redox properties.

2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.


Author(s):  
Mardia T. El Sayed ◽  
Ibrahim H.I. Habib ◽  
Nermien M. Sabry ◽  
Sergey A. Pisarev ◽  
Mohamed El-Naggar ◽  
...  

Absorption spectra of tetrahydro[3,2-b]indolo-carbazoles (THICZs) with various molecular size and alkyl tails have been recorded in various solvents in the range between 200 to 600 nm. The photo physical behaviour of dissolved THICZs depends on the nature of its environment. The solvatochromic behaviours of THICZs and solvent solute interactions can be analysed by means of linear solvation energy relationships concept proposed by Kamlet and Taft. Compound 4 show excellent properties for sensing small molecules. The electrochemical behaviour of some THICZs was investigated at carbon paste electrode where two electrode reactions were involved, irreversible oxidation-one electron transfer and quasi-reversible redox reactions forming phenolic followed by quinolone moiety electro active species. The DFT-calculated molecular orbital energies (B3LYP/6-31G) and HOMO-LUMO gaps for some presented indolocarbazoles have been performed.


1979 ◽  
Vol 44 (5) ◽  
pp. 1540-1551 ◽  
Author(s):  
Jaro Komenda ◽  
Jiří Huzlík

Compounds of the type of 2-(4'-nitrobenzoyl)methylene-3-ethylbenzothiazoline (I) and 2-bis-(p-nitrobenzoyl)methylene-3-ethylbenzothiazoline (II) were studied polarographically and by ESR spectroscopy to obtain informations about their electrochemical and follow-up reactions and their conformation. Whereas with compounds of the type I the conjugation in their molecules is preserved, with type II the coplanarity of the molecules is disturbed, which is manifested in the values of the splitting constants of the ESR spectra and a slow electron transfer between both nitrophenyl substituents. These conclusions are supported by NMR spectroscopic studies.


Author(s):  
Frederico F Martins ◽  
Ángel Sánchez-González ◽  
Jose Lanuza ◽  
Haralampos N. Miras ◽  
Xabier Lopez ◽  
...  

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Paola Riente ◽  
Mauro Fianchini ◽  
Patricia Llanes ◽  
Miquel A. Pericàs ◽  
Timothy Noël

AbstractThe importance of discovering the true catalytically active species involved in photocatalytic systems allows for a better and more general understanding of photocatalytic processes, which eventually may help to improve their efficiency. Bi2O3 has been used as a heterogeneous photocatalyst and is able to catalyze several synthetically important visible-light-driven organic transformations. However, insight into the operative catalyst involved in the photocatalytic process is hitherto missing. Herein, we show through a combination of theoretical and experimental studies that the perceived heterogeneous photocatalysis with Bi2O3 in the presence of alkyl bromides involves a homogeneous BinBrm species, which is the true photocatalyst operative in the reaction. Hence, Bi2O3 can be regarded as a precatalyst which is slowly converted in an active homogeneous photocatalyst. This work can also be of importance to mechanistic studies involving other semiconductor-based photocatalytic processes.


2001 ◽  
Vol 3 (3) ◽  
pp. 329-332 ◽  
Author(s):  
Dirk V. Deubel ◽  
Jörg Sundermeyer ◽  
Gernot Frenking

2018 ◽  
Vol 8 (19) ◽  
pp. 5073-5080 ◽  
Author(s):  
Xavier Frogneux ◽  
Ferenc Borondics ◽  
Stéphane Lefrançois ◽  
Florian D'Accriscio ◽  
Clément Sanchez ◽  
...  

Depending on the ligand, ligand-induced leaching of copper nanoparticles may produce catalytically active species for the reduction of benzaldehyde.


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