AbstractSeCF2 is prepared on a preparative scale reacting AII3 with Hg(SeCF3)2 in octamethyl-cyclotetrasiloxane. It adds MF [M = Cs, Tl, [(CH3)4N] and Ag] to form MSeCF3. AgSeCF3 was also synthesized from AgF and B(SeCF3)3. Under the influence of sunlight SeCF2 dissolved in CFCI3 dimerizes quantitatively to 2,2,4,4-tetrafluoro-1,3-diselenetane, which above 360 °C pyrolyses to the monomer. The cyclic dimer reacts with B(SeCF3)3 to give (CF3Se)2CSe. The reaction of AgSeCF3 with CFnCl3-nSCl leads to CF3SeSCFnCl3-n (n = 1, 2, 3). IR, NMR and mass spectra of the newly prepared compounds were presented.
Die Reaktionen des Ag‐seleninats (I) mit den halogenierten Methansulfenylchloriden (II) bei niedrigen Temp. fuhren zu den Selenosulfen‐Verbindungen (III).
Abstract Selenophosgene was prepared for the first time by vacuum pyrolyses of 2,2,4,4-tetra-chloro-1,3-diselenetane. The dark blue compound, stable only below -130 °C, was characterized by mass, low temperature UV, IR matrix and Raman matrix spectroscopy.
Umsetzungen von CF3SeBr mit NH3 führen je nach Reaktionsbedingungen zu (CF3Se)nNH3−n (n = 1, 2 und 3). Mit CF3SNCO reagiert CF3SNH2 zu CF3SNH · CO · NHSeCF3; (CF3Se)3N setzt sich mit P(C6H5)3 zu CF3SeN P(C6H5)3 um. Die Synthese von (CF3Se)3E (E = P, As) erfolgt aus Hg(SeCF3)2 und EBr3 in CS2. Analog erhält man aus Hg(SeCF3)2 und P2J4 in CS2 ein (CF3Se)2PP(SeCF3)2, das mit (CF3Se)3P verunreinigt ist. C6H5P(SeCF3)2 entsteht aus C6H5PJ2 bzw. C6H5P(J)(J)C6H5 und Hg(SeCF3)2 oder aber durch Umsetzung von (C6H5P)5 mit CF3SeSeCF3. IR‐, 1H‐, 19F‐, 31P‐, 77Se‐NMR und Massenspektren werden angegeben.
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