The direct electrochemical synthesis of triphenylphosphine adducts of Group IB monohalides

1981 ◽  
Vol 59 (18) ◽  
pp. 2714-2718 ◽  
Author(s):  
Masood Khan ◽  
Colin Oldham ◽  
Dennis G. Tuck
Keyword(s):  
Current Efficiency ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Benzyl Chloride ◽  
Reaction Pathway ◽  
Hydrogen Halide ◽  
Structural Studies ◽  
X Ray ◽  
Acetonitrile Solutions

The electrochemical oxidation of copper, silver, or gold into acetonitrile solutions of benzyl chloride or hydrogen halide plus triphenylphosphine leads to the formation of the adducts MXLn (M = Cu, Ag, Au; X = Cl, Br, I; L = Ph3P; n = 1, 1.5, 2; not all combinations). The value of n depends markedly on the mole ratio Ph3P:dissolved metal. The reaction pathway is discussed in the light of measurements of current efficiency. The results of X-ray structural studies of AuCl•L and AuClL2 are briefly reported.

The direct electrochemical synthesis of some metal derivatives of lapachol

1997 ◽  
Vol 75 (5) ◽  
pp. 499-506 ◽  
Author(s):  
E.H. De Oliveira ◽  
G.E.A. Medeiros ◽  
C. Peppe ◽  
Martyn A. Brown ◽  
Dennis G. Tuck
Keyword(s):  
Electrochemical Oxidation ◽  
Copper Atom ◽  
Electrochemical Synthesis ◽  
Acetonitrile Solution ◽  
Triclinic Space Group ◽  
X Ray ◽  
Metal Anode ◽  
X Ray Crystallography ◽  
Metal Derivatives ◽  
Derivatives Of

The electrochemical oxidation of a sacrificial metal anode (M = Zn, Cd, Cu) in an acetonitrile solution of 2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone, lapachol, C15H14O3 (=HL) gives ML2. The results are in keeping with earlier work on direct electrochemical synthesis in related systems. Adducts with 2,2′-bipyridine (bpy) and N,N,N′,N′-tetramethylethanediamine (tmen) have also been prepared. The structure of the 2,2′-bipyridine adduct of Cu(lapacholate)2 has been established by X-ray crystallography. The parameters are triclinic, space group [Formula: see text], a = 12.748(59) Å, b = 13.859(49) Å, c = 11.770(59) Å, α = 108.30(4)°, β = 108.08(3)°, γ = 68.94(3)°, Z = 2, R = 0.059 for 2256 unique reflections. The copper atom is in a distorted CuN2O2O2′ environment. The mechanism of the formation of this Cu(lapacholate)2 is discussed. Keywords: electrochemical synthesis, lapachol, X-ray crystallography, copper(II) complex.

scholarly journals Wastewater Minimization in Indirect Electrochemical Synthesis of Phenylacetaldehyde

2002 ◽  
Vol 2 ◽  
pp. 48-52 ◽  
Author(s):  
Zhirong Sun ◽  
Xiang Hu ◽  
Ding Zhou
Keyword(s):  
Sulfuric Acid ◽  
Current Efficiency ◽  
Electrochemical Oxidation ◽  
Acid Concentration ◽  
Electrochemical Synthesis ◽  
Chemical Process ◽  
Sulfuric Acid Concentration ◽  
High Yield ◽  
High Current ◽  
High Current Efficiency

Wastewater minimization in phenylacetaldehyde production by using indirect electrochemical oxidation of phenylethane instead of the seriously polluting traditional chemical process is described in this paper. Results show that high current efficiency of Mn(III) and high yield of phenylacetaldehyde can be obtained at the same sulfuric acid concentration (60%). The electrolytic mediator can be recycled and there will be no waste discharged.

The direct electrochemical synthesis of thiolato complexes of cobalt and nickel, and the crystal structure of bis(phenylthiolato)bis(1,10-phenanthroline)cobalt(III) perchlorate

1988 ◽  
Vol 66 (9) ◽  
pp. 2151-2156 ◽  
Author(s):  
Raj K. Chadha ◽  
Rajesh Kumar ◽  
Jaime Romero Lopez-Grado ◽  
Dennis G. Tuck
Keyword(s):  
Crystal Structure ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Crystallographic Analysis ◽  
High Yield ◽  
X Ray ◽  
Metal Anode ◽  
Aerial Oxidation ◽  
Perchlorate Salt ◽  
Cobalt And Nickel

Cobalt(II) and nickel(II) thiolates, M(SR)2, can be prepared in high yield by the electrochemical oxidation of a metal anode in an acetonitrile or acetone solution of RSH (R = C6H5, o-CH3C6H4, 2-C10H7, 2,3,4,5-C6F4H; not all combinations). When 2,2-bipyridine or 1,10-phenanthroline (=L) is added to the electrolyte phase, the products are the adducts M(SR)2L2. In the case of Co(SC6H5)2(phen)2, aerial oxidation leads to the formation of the cobalt(III) cation [Co(SC6H5)2(phen)2]+, isolated as the perchlorate salt. X-ray crystallographic analysis showed that this cation has a cis-CoS2(N2)2 kernel.

scholarly journals Direct Electrochemical Synthesis of Pyrimidine-2-thionato Complexes of Zinc(II) and Cadmium(II): The Crystal Structure of (1,10-Phenanthroline)bis(pyrimidine-2-thionato)cadmium(II)

1992 ◽  
Vol 47 (8) ◽  
pp. 1067-1074 ◽  
Author(s):  
R. Castro ◽  
M. L. Durán ◽  
J. A. García-Vázquez ◽  
J. Romero ◽  
A. Sousa ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Nitrogen Atom ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Electrochemical Cell ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Cadmium Atom ◽  
Distorted Octahedral ◽  
Acetonitrile Solutions

Zn(pymt)2 and Cd(pymt)2 complexes have been obtained by electrochemical oxidation of anodic zinc or cadmium in acetonitrile solutions of pyrimidine-2-thione (Hpymt). When 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrochemical cell, the adducts [M(pymt)2(bipy)], or [M(pymt)2(phen)] (M = Zn or Cd) were obtained. Crystals of [Cd(pymt)2phen] are orthorhombic, with a = 9.882(2), b = 12.491(1), c = 16.513(2)Å, space group P212121 and Z = 4. The cadmium atom has distorted octahedral geometry, and one nitrogen atom of each pyrimidine-2-thiolato ligand is not coordinated.

The fortuitous direct electrochemical synthesis of some copper(I) complexes

1981 ◽  
Vol 59 (1) ◽  
pp. 62-64 ◽  
Author(s):  
Farouq F. Said ◽  
Dennis G. Tuck
Keyword(s):  
Complex Formation ◽  
Current Efficiency ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Solution Chemistry ◽  
Formation Processes ◽  
Halide Complexes

The electrochemical oxidation of copper in the presence of RX (R = CH3, C6H5, C6H5CH2; X = Cl, Br, I, not all combinations) and either 2,2′-bipyridine or (C2H5)4NX gives rise to neutral or anionic copper(I) halide complexes. The current efficiency shows that CuX is produced at the anode; the subsequent solution chemistry influences the complex formation processes.

Electrochemistry of 1,2,5-thiadiazole 1,1-dioxide derivatives with 3,4 substituents presenting separated, connected, and fused Pi-systems

1999 ◽  
Vol 77 (4) ◽  
pp. 511-517 ◽  
Author(s):  
Esther Lea Svartman ◽  
José Alberto Caram ◽  
María Virginia Mirífico ◽  
Enrique Julio Vasini
Keyword(s):  
Theoretical Chemistry ◽  
Structural Studies ◽  
Spectroscopy Data ◽  
X Ray ◽  
X Ray Crystallography ◽  
Organic Electrochemistry ◽  
Pi Systems ◽  
Voltammetric Behavior ◽  
Bulk Electrolysis ◽  
Acetonitrile Solutions

The voltammetric electroreduction properties of 1,2,5-thiadiazole 1,1-dioxide derivatives with different 3,4 substituents have been investigated in aprotic (mainly acetonitrile) solvent solution. The 3,4 substituents, selected according to the characteristics of their π-system, were phenanthro-9,10 (connected π-system) and acenaphtho-1,2 (fused π-system). New measurements are also presented for 3,4-diphenyl (separated π-systems). The basic properties of the substrates were investigated through voltammetry in acidic acetonitrile solutions. The substrates were more easily electroreduced (between -0.6 and -1.0 V vs. Ag/Ag+, acetonitrile solvent) than the parent (non-1,1-dioxide) heterocycles (which are electroreduced at ca. -2.5 V). They were also more easily electroreduced (by ca. 0.4 V) than the corresponding diketones (benzil, 9,10-phenanthrenequinone, and acenaphthenequinone). The influence on voltammetric behavior of the electron-withdrawing properties of the 1,2,5-thiadiazole 1,1-dioxide ring and that of the structure of the molecules was analyzed in light of previous structural studies by X-ray crystallography and theoretical chemistry calculations. Bulk electrolysis experiments in acidic acetonitrile solutions of the phenanthro[9,10-c] derivative produced its previously unreported dihydrogenated derivative (thiadiazoline), which oxidizes easily. Infrared spectroscopy data suggested that the structure of this compound differs from that of 3,4-diphenyl-1,2,5-thiadiazoline 1,1-dioxide.Key words: organic electrochemistry, 1,2,5- thiadiazoles, structure-reactivity relations.

The electrochemical synthesis of β-diketonato complexes of cadmium(II), and their adducts; the crystal and molecular structure of Cd(acac)2phen

1983 ◽  
Vol 61 (9) ◽  
pp. 2141-2146 ◽  
Author(s):  
Luis Bustos ◽  
James H. Green ◽  
J. Lawrence Hencher ◽  
Masood A. Khan ◽  
Dennis G. Tuck
Keyword(s):  
Molecular Structure ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Good Yield ◽  
Room Temperature ◽  
Crystal And Molecular Structure ◽  
Electrolytic Solution ◽  
X Ray ◽  
Subsequent Addition

The cadmium β-diketonate complexes Cd(RCOCHCOR′)2 (R = CH3, R′ = CH3; R = CF3 R′ = CH3, i-C3H7, i-C4H9, t-C4H9, C6H5, 2-naphthyl) can be prepared in good yield by the direct room temperature electrochemical oxidation of the metal into a solution of the parent diketone in acetonitrile. Adducts of the type Cd(RCOCHCOR′)2L (L = 2,2′-bipyridine, 1,10-phenanthroline, N,N,N′,N′-tetramethylethylenediamine) can be prepared insitu, or by subsequent addition of the ligand to the electrolytic solution. X-ray studies show that the molecular structure of both Cd(acac)2phen and Cd(CF3COCHCOC6H5)2phen is based on a CdO4N2 kernel, distorted from octahedral stereochemistry by the bite of the ligands.

Ribosome Structural Organization

1974 ◽  
Vol 32 ◽  
pp. 332-333
Author(s):  
James A. Lake
Keyword(s):  
Ribosomal Proteins ◽  
Structural Organization ◽  
Three Dimensional ◽  
Small Subunit ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Specific Antibodies ◽  
X Ray ◽  
E Coli ◽  
Complete Sequences

The understanding of ribosome structure has advanced considerably in the last several years. Biochemists have characterized the constituent proteins and rRNA's of ribosomes. Complete sequences have been determined for some ribosomal proteins and specific antibodies have been prepared against all E. coli small subunit proteins. In addition, a number of naturally occuring systems of three dimensional ribosome crystals which are suitable for structural studies have been observed in eukaryotes. Although the crystals are, in general, too small for X-ray diffraction, their size is ideal for electron microscopy.

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