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 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 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 phenylselenolato complexes of some main group and late transition elements

1989 ◽  
Vol 67 (1) ◽  
pp. 127-129 ◽  
Author(s):  
Rajesh Kumar ◽  
Dennis G. Tuck
Keyword(s):  
Aqueous Solutions ◽  
Electrochemical Synthesis ◽  
Nmr Spectra ◽  
Electrochemical Cell ◽  
Main Group ◽  
Diphenyl Diselenide ◽  
Transition Elements ◽  
Late Transition Metals ◽  
Late Transition ◽  
High Yields

The electrochemical oxidation of anodes of selected Main Group or late transition metals (M) in non-aqueous solutions of diphenyl diselenide gives the corresponding M(SePh)n compounds in high yields (M = Zn, Cd, n = 2; M = Cu, Ag, Tl, n = 1; M = Sn, n = 4). The addition of either 1,10-phenanthroline or triphenylphosphine to the electrochemical cell yields adducts in the case of cadmium and copper. The 77Se nmr spectra have been recorded. Keywords: electrochemistry, synthesis, phenylselenates, 77Se nmr spectra.

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

1984 ◽  
Vol 62 (9) ◽  
pp. 1701-1704 ◽  
Author(s):  
N. Kumar ◽  
Dennis G. Tuck
Keyword(s):  
Nitric Acid ◽  
Aqueous Solutions ◽  
Ethyl Acetate ◽  
Electrochemical Oxidation ◽  
Electrochemical Synthesis ◽  
Dinitrogen Tetroxide ◽  
Nitrate Complexes ◽  
Nitrate Species

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.

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.

scholarly journals Recent Advances in Metal Catalyst Design for CO2 Hydroboration to C1 Derivatives

Catalysts ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 58
Author(s):  
Sylwia Kostera ◽  
Maurizio Peruzzini ◽  
Luca Gonsalvi
Keyword(s):  
Transition Metals ◽  
Chemical Synthesis ◽  
Building Block ◽  
Co2 Reduction ◽  
Main Group ◽  
Catalyst Design ◽  
Metal Catalyst ◽  
Simple Molecule ◽  
Recent Advances ◽  
Renewable Feedstock

The use of CO2 as a C1 building block for chemical synthesis is receiving growing attention, due to the potential of this simple molecule as an abundant and cheap renewable feedstock. Among the possible reductants used in the literature to bring about CO2 reduction to C1 derivatives, hydroboranes have found various applications, in the presence of suitable homogenous catalysts. The current minireview article summarizes the main results obtained since 2016 in the synthetic design of main group, first and second row transition metals for use as catalysts for CO2 hydroboration.

The use of main-group elements to mimic catalytic behavior of transition metals I: reduction of dinitrogen to ammonia catalyzed by bis(Lewis base)borylenium diradicals

2020 ◽  
Vol 22 (48) ◽  
pp. 28423-28433
Author(s):  
Yu Wang ◽  
Chun-Guang Liu
Keyword(s):  
Transition Metals ◽  
Main Group ◽  
Lewis Base ◽  
Main Group Elements ◽  
Catalytic Behavior ◽  
Metal Free

An emerging class of compounds, bis(Lewis base)borylenium diradicals with an electron-rich boron(i) center, are potential metal-free catalysts for dinitrogen activation and reduction.

ChemInform Abstract: Multiple Bonds Between Main Group Elements and Transition Metals. Part 84. Organoosmium Oxides: Efficient Syntheses and Structures.

ChemInform ◽  
2010 ◽  
Vol 22 (10) ◽  
pp. no-no
Author(s):  
W. A. HERRMANN ◽  
S. J. EDER ◽  
P. KIPROF ◽  
K. RYPDAL ◽  
P. WATZLOWIK
Keyword(s):  
Transition Metals ◽  
Main Group ◽  
Multiple Bonds ◽  
Main Group Elements
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