The reactions of (dpp-bian)Mg(thf) 3 (1) {dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene} with 0.5 molar equivalents of RS-SR (R = Bz, sBu, C(S)NMe 2 ) occur with a cleavage of the S-S bond to afford monosulfide complexes (dpp-bian)Mg(SBz)(dme) (2), (dpp-bian)Mg[S(sBu)]-(dme) (3), and (dpp-bian)Mg[SC(S)NMe 2 ](thf) (4). Compounds 2, 3, and 4 are paramagnetic due to the presence of dpp-bian radical-anions that are formed in the course of oneelectron transfer from the dpp-bian dianion in 1 to the sulfurcontaining substrate. Reduction of BzS-SBz with gallane (dpp-bian)Ga-Ga(dpp-bian) (5) gives a mononuclear Ga III
Redox isomerism is observed for a lanthanide complex for the first time. Upon lowering the temperature, an electron of [{(dpp-bian)Yb(μ-Cl)(dme)}(2)] (1) is transferred from the metal to the ligand (see picture), giving rise to marked shortening of Yb-N bonds and a hysteretic jump in the magnetic moment. The crystal packing is of a crucial importance, as two other crystal modifications of 1 do not undergo this effect.
Ytterbium reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (1, dpp-Bian) in 1,2-dimethoxyethane (DME) to give complex (dpp-Bian)Yb(DME)(2) (2). Oxidation of 2 with an 0.5 mol equivalent of dibromostilbene affords dimeric compound [(dpp-Bian)Yb(DME)(mu-Br)](2) (3). Molecular structures of 2 and 3 were determined by single-crystal X-ray analysis. In complex 3 in a DME solution, a temperature-dependent reversible intramolecular electron transfer between the ligand and the metal takes place.
The aim of this paper is to demonstrate the possibilities of anaerobic sludge cells immobilized into poly(vinyl alcohol) cryogel for the methanogenic conversion of various lignocellulosic waste and other media containing antibiotics (ampicillin, kanamycin, benzylpenicillin) or pesticides (chlorpyrifos or methiocarb and its derivatives). It was established that the immobilized cells of the anaerobic consortium can be stored frozen for at least three years while preserving a high level of metabolic activity. The cells after the long-term storage in an immobilized and frozen state were applied for the methanogenesis of a wide number of wastes, and an increase in both methane yield and methane portion in the produced biogas as compared to the conventionally used suspended anaerobic sludge cells, was ensured. It was shown that the “additional” introduction of bacterial Clostridium acetobutylicum, Pseudomonas sp., Enterococcus faecalis cells (also immobilized using same support) improves characteristics of methanogenesis catalyzed by immobilized anaerobic sludge.
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