10387-40-3Relevant articles and documents
Sulphur-sulphur, sulphur-selenium, selenium-selenium and selenium-carbon bond activation using Fe3(CO)12: An unexpected formation of an Fe2(CO)6 complex containing a μ2,κ3-C,O,Se-ligand
Trautwein, Ralf,Abul-Futouh, Hassan,G?rls, Helmar,Imhof, Wolfgang,Almazahreh, Laith R.,Weigand, Wolfgang
, p. 12580 - 12593 (2019)
Three diiron hexacarbonyl complexes containing dithiolato (5), diselenolato (6), and selenolato-thiolato ligands (7), respectively, have been prepared as [FeFe]-hydrogenase mimics. Treatment of Fe3(CO)12 with one equivalent of the corresponding 5-membered heterocycles 1, 3 and 4 in toluene at reflux afforded the corresponding complexes 5-7. The reaction of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane with in situ generated Na2Se2 results in the formation of 8,8-dimethyl-7,9-dioxa-2,3-diselenaspiro[4.5]decane (1) and traces of 7,7-dimethyl-6,8-dioxa-2-selenaspiro[3.4]nonane (2). Alternatively, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane reacts with in situ generated Na2Se yielding compound 2 in 26% yield. When Fe3(CO)12 reacts under reflux with the selenaspiro compound 2 in toluene, the unique diiron complex, [Fe2(CO)6{μ2,κ3-Se,C,O-SeCH2C7H12O2}] (8), is obtained as a result of an initial selenium-carbon bond activation. Compounds 5, 6, 7, and 8 were characterized by IR, 1H, 13C{1H}, and 77Se{1H} NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray single-crystal structure analysis. The chiral complex 8 shows a coordination of the O atom at the dioxane ring to one Fe atom and the O-CH- carbanionic group to the other Fe atom. Furthermore, we investigated the redox properties and the catalytic behaviour of complexes 5-8 in the presence of AcOH as a source of protons. The reduction of complexes 5-7 is accompanied by a chemical process resulting in an overall two-electron transfer at their primary reduction wave. This observation is consistent with an ECE reduction (E = electrochemical process, C = chemical process), while each reduction event in the case of complex 8 involves simple transfer of one electron. Moreover, high level DFT calculations were performed on neutral 8 and its reduction products 8- and 82-.
Thioacids and thioacid salts for determining the enantiomeric excess of chiral compounds containing an electrophilic carbon center
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, (2009/07/25)
The invention provides novel chiral compounds including 2-methoxy-2-trifluoromethylphenylacetic thioacid useful to react with and analyze other chiral compounds that have an electrophilic chiral carbon center.
A Convenient Preparation of Anhydrous Alkali Metal Thiocarboxylates
Kato, Shinzi,Oguri, Motohiro,Ishida, Masaru
, p. 1585 - 1590 (2007/10/02)
A series of alkali metal thiocarboxylates (1-5) were found to be readily obtained in high yields by the reaction of thiocarboxylic acids with metal hydrides (LiH, NaH, KH), and rubidium or caesium acetates, respectively.Their physical properties were disclosed. - Keywords: Lithium Thiocarboxylates, Sodium Thiocarboxylates, Potassium Thiocarboxylates, Rubidium Thiocarboxylates, Caesium Thiocarboxylates
