The direct electrochemical synthesis of some thorium(IV) nitrate complexes

The electrochemical oxidation of thorium in either nitric acid/tri-n-butyl phosphate (TBP) or dinitrogen tetroxide/ethyl acetate/acetonitrile media gives rise to non-aqueous solutions of thorium(IV) nitrate species. The only neutral adduct which could be obtained from HNO3/TBP solution was Th(NO3)4•8dmso (dmso = dimethylsulphoxide). Salts of [Th(NO3)6]2− with Et4N+, [(bpyH)3NO3]2+, and [(phenH)3NO3]2+ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) were also prepared by this route. Solutions in N2O4/EtOAc/CH3CN yield Th(NO3)4, and neutral adducts with dmso, bpy, phen, Ph3PO, and pyridine-N-oxide.

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

Canadian Journal of Chemistry ◽

10.1139/v87-224 ◽

1987 ◽

Vol 65 (6) ◽

pp. 1336-1342 ◽

Cited By ~ 60

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

Canadian Journal of Chemistry ◽

10.1139/v87-157 ◽

1987 ◽

Vol 65 (5) ◽

pp. 928-932 ◽

Cited By ~ 15

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.

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147. Electrical conductances of solutions in nitric acid. Part III. Solutions of dinitrogen tetroxide

Journal of the Chemical Society (Resumed) ◽

10.1039/jr9590000734 ◽

1959 ◽

pp. 734 ◽

Cited By ~ 3

Author(s):

J. D. S. Goulden ◽

W. H. Lee ◽

D. J. Millen

Keyword(s):

Nitric Acid ◽

Electrical Conductances ◽

Dinitrogen Tetroxide

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The direct electrochemical synthesis of some metal derivatives of lapachol

Canadian Journal of Chemistry ◽

10.1139/v97-058 ◽

1997 ◽

Vol 75 (5) ◽

pp. 499-506 ◽

Cited By ~ 15

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.

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