The electrochemical synthesis of organometallic halides of titanium, zirconium, and hafnium

1980 ◽  
Vol 58 (16) ◽  
pp. 1673-1677 ◽  
Author(s):  
Farouq F. Said ◽  
Dennis G. Tuck
Keyword(s):  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
A Cell ◽  
Titanium Zirconium

The electrochemical oxidation of titanium, zirconium, or hafnium (= M) in a cell containing an organic halicie RX results in the formation of an organometallic halide of the metal concerned. These compounds are conveniently isolated as adducts of acetonitrile or 2,2′-bipyridine(bipy) also présent in the electrolyte phase. The products most commonly isolated are the [Formula: see text], but other species were obtained in certain cases. Possible reasons for these findings are discussed.

Direct electrochemical synthesis of neutral and anionic chloro- and bromo-complexes of titanium, zirconium, and hafnium

1977 ◽  
Vol 55 (22) ◽  
pp. 3882-3886 ◽  
Author(s):  
Jacob J. Habeeb ◽  
Farouq F. Said ◽  
Dennis G. Tuck
Keyword(s):  
Reaction Mechanism ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Good Yield ◽  
Direct Synthesis ◽  
Solution Phase ◽  
Tetraalkylammonium Salts ◽  
Titanium Zirconium

Electrochemical oxidation of titanium, zirconium, or hafnium(IV) in the presence of a solution of chlorine or bromine (X) in acetonitrile (L) leads to direct synthesis of MX4L2 species in good yield. These compounds are easily transformed into other neutral adducts. On addition of tetraalkylammonium salts to the solution phase, the products are the salts (R4N)MCl5 or (R4N)2MBr6, except that with titanium Et4NTiBr4 was also formed under some conditions. The advantages of this method are discussed, and a possible reaction mechanism proposed.

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.

Electrochemical synthesis of 1-N-phenyl-4-(sulfonyl)benzene-1,2-diamine derivatives: a mild and regioselective protocol

2016 ◽  
Vol 40 (6) ◽  
pp. 5442-5447 ◽  
Author(s):  
Mahnaz Sharafi-Kolkeshvandi ◽  
Davood Nematollahi ◽  
Farzad Nikpour ◽  
Eslam Salahifar
Keyword(s):  
Aqueous Solution ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Regioselective Synthesis ◽  
Sulfinic Acids

Regioselective synthesis of 1-N-phenyl-4-(arylsulfonyl)benzene-1,2-diamine derivatives was carried out by the electrochemical oxidation of 2-aminodiphenylamine in aqueous solution in the presence of sulfinic acids as nucleophiles.

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 neutral and anionic complexes of thorium(IV)

1982 ◽  
Vol 60 (20) ◽  
pp. 2579-2582 ◽  
Author(s):  
N. Kumar ◽  
Dennis G. Tuck
Keyword(s):  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Good Yield ◽  
Electrochemical Methods ◽  
Chelate Complexes ◽  
Anionic Complexes ◽  
One Step

The electrochemical oxidation of thorium into solutions of halogen (X2; X = Cl, Br) in acetonitrile yields the adducts ThX4•4CH3CN in good yield. With solutions of X2 + R4NX, the products are (R4N)2ThX6. Neutral chelate complexes such as Th(acac)4 (acac = 2,4-pentanedionate) can also be prepared in a one-step synthesis from the metal, but cationic complexes could not be obtained by electrochemical methods.

The direct electrochemical synthesis of thiolato complexes of copper, silver, and gold; the molecular structure of [Cu(SC6H4CH3-o)(1,10-phenanthroline)]2•CH3CN

1987 ◽  
Vol 65 (6) ◽  
pp. 1336-1342 ◽  
Author(s):  
Raj K. Chadha ◽  
Rajesh Kumar ◽  
Dennis G. Tuck
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Aqueous Solutions ◽  
Electrochemical Oxidation ◽  
Copper Atom ◽  
Electrochemical Synthesis ◽  
High Yield ◽  
Space Group ◽  
Anodic Copper

The electrochemical oxidation of anodic copper or silver (= M) into non-aqueous solutions of RSH (R = alkyl, axyl) gives MISR as insoluble materials in high yield. In the presence of 1,10-phenanthroline (= L), the products are MISR•phen for M = Cu, but not Ag. Gold resists oxidation under such conditions, and AuISR (R = n-C4H9, C6H5) was obtained in only poor yield. The crystal structure of the solvated dimeric adduct [Cu(SC6H4CH3-o)•phen]2•CH3CN is triclinic, with a = 10.682(3) Å, b = 11.729(4) Å, c = 15.608(5) Å, α = 76.87(2)°, β = 76.35(2)°, γ = 68.07(2)°, V = 1742(1) Å3, Z = 2 and space group [Formula: see text]. The structure is based on a folded Cu2S2 ring with an unusually short Cu—Cu distance of 2.613(3) Å Each copper atom has CuS2N2 pseudo-tetrahedral stereochemistry, with Cu—S = 2.337 Å(av) and Cu—N = 2.10 Å(av).

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 Electrochemical Synthesis of 3a-Bromofuranoindolines and 3a-Bromopyrroloindolines Mediated by MgBr2

2019 ◽  
Author(s):  
Ju Wu ◽  
Hussein Abou Hamdan ◽  
Régis Guillot ◽  
Cyrille Kouklovsky ◽  
Guillaume Vincent
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Environmentally Friendly ◽  
Electrochemical Approach ◽  
Tryptophan Derivatives

<div> <p>We report an efficient and environmentally friendly electrochemical approach to perform the bromo cyclization of tryptophol, tryptamine and tryptophan derivatives. The 3a-bromofuranoindolines and 3a-bromopyrroloindolines obtained are of interest in the total synthesis of natural products. This dearomative procedure relies on the generation of an electrophilic bromine reagent by the electrochemical oxidation of MgBr<sub>2</sub>. No organic byproducts are generated with this protocol which avoids the use of an additional electrolyte.</p> </div>

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.

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