Mehrstufige reversible Redoxsysteme, LIV. Leitfähige CT-Komplexe des Tetrathiafulvalens (TTF) mit Tetracyanchinodimethan (TCNQ) undN,N′-Dicyanbenzochinondiimin (DCNQI) - ein Vergleich (original) (raw)
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Chemische Berichte, 1991
Multi-Step Redox Systems, LVI').-Crystal Structures and Conductivities of the CT Complexes TTF/2-X-5-Me-DCNQI (X = C1. Br, I) from Tetrathiafulvalene and 2-Halogeno-N,N'-dicyano-5-methyl-l,4-benzoquinone Diimine In contrast to microcrystalline powders single crystals of the ment of donor and acceptor molecules within the crystal lattitle complexes show low conductivities ((T < These properties are based on a peculiar mixed stack arrange-Scm-I). tice (space group PZ,/n). 1. Elektrische Leitfahigkeiten einiger TTFDCNQI-Komplexe U Abb. 3. Kristallpackung in der Elementarzelle von TTF/2-Br-5-Me-DCNQI, Blickrichtung parallel zur a,c-Ebene, ungeordnete CHJ Br als Kugeln gleicher GroDe dargestellt
Chemische Berichte, 1990
Reactions of 2.2,4,4-Tetrakis(trifluoromethyl)-1.3-dithfetane phosphane Gold(1) Complex of a Thiazoline-4-thiolate 2,2,4,4-Tetrakis(trifluoromethyl)-1,3-dithietane (1) reacts with KNCS to yield the potassium salt of 4-mercapto-2,2,5,5-tetrakis(trifluoromethy1)-A3-thiazoline (2). An oxidative workup procedure results in the formation of the disulfide 6. The salt 2 reacts with methyl bromoacetate, benzyl bromide, 3-bromo-1 -phenylpropene, and 1,3-diiodopropane to form the thioethers 3-5 and 7, respectively. Protonation of 2 results in the formation of the thio-with KNCS and KNCO -Crystal Structure of a Triphenyllactam 9. Disulfide 6 reacts with C12 in the presence of FeC13 to yield the sulfenyl chloride 8. C-S bond formation (410) is observed by treating 8 with Me,SiCN. The gold(1) complex 11 is formed from 2 and Ph,PAuCI. 11 crystallizes in the monoclinic space group P2!/n and contains a linear P-Au-S unit. The reaction of 1 with KNCO leads after protonation to the perfluorinated lactam 12 and the cyanuric acid derivative 13.
Zeitschrift für Naturforschung B, 1986
Zeitschrift für Naturforschung B, 1992
In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alky...
Zeitschrift für Naturforschung B, 1991
In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)). Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identica...