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 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.

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 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.

The direct electrochemical synthesis of dialkyldithiocarbamate and diethyldithiophosphate complexes of main group and transition metals

1987 ◽  
Vol 65 (5) ◽  
pp. 928-932 ◽  
Author(s):  
Corrado Geloso ◽  
Rajesh Kumar ◽  
Jaime Romero Lopez-Grado ◽  
Dennis G. Tuck
Keyword(s):  
Transition Metals ◽  
Aqueous Solutions ◽  
Electrochemical Oxidation ◽  
Secondary Amine ◽  
Electrochemical Synthesis ◽  
Good Yield ◽  
Carbon Disulphide ◽  
Main Group ◽  
Sacrificial Anodes

Dialkyldithiocarbamate derivatives (R2NCS2)nM of a number of metals (M = Fe, Co, Ni, Cu, Ag, Zn, Cd, In, Tl) have been synthesised in good yield by electrochemical oxidation of appropriate sacrificial anodes in non-aqueous solutions of either the corresponding tetraalkylthiuram disulphide (R2NCS2)2 (R = Me, Et) or a mixture of carbon disulphide plus the secondary amine R2NH (R = Et, i-Pr; R2NH = piperidine). Similar experiments with solutions of (EtO)2P(S)SH (= HL) gave MLn•derivatives (M = Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Tl) while in the presence of HL + 1,10-phenanthroline, MLn•phen derivatives were obtained for M = V, Mn, Fe, Co, Zn, and Ga.

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 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).

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