Abstract
An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.
| Original language | English |
|---|---|
| Pages (from-to) | 340-350 |
| Number of pages | 11 |
| Journal | Inorganic Chemistry |
| Volume | 17 |
| Issue number | 2 |
| State | Published - 1978 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
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Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV). / Wheeler, S. H.; Mattson, Bruce M.; Miessler, G. L.; Pignolet, L. H.
In: Inorganic Chemistry, Vol. 17, No. 2, 1978, p. 340-350.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV)
AU - Wheeler, S. H.
AU - Mattson, Bruce M.
AU - Miessler, G. L.
AU - Pignolet, L. H.
PY - 1978
Y1 - 1978
N2 - An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.
AB - An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.
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M3 - Article
VL - 17
SP - 340
EP - 350
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 2
ER -