Bis(perfluor‐n‐hexyl)‐ und Bis(perfluor‐n‐octyl)cadmium: Darstellung, Eigenschaften, NMR‐spektroskopische und massenspektrometrische Untersuchungen

Abstract

Die Perfluoralkylcadmium‐Verbindungen Cd(C6F13)2 und Cd(C8F17)2 werden sowohl unkomplexiert als auch als Komplexe mit DMF, CH3CN, Glyme und Diglyme dargestellt. Die Reaktionsgeschwindigkeit der Cd(Rf)2‐Verbindungen mit PhHgCl nimmt mit der durch Leitfähigkeitsmessungen in verschiedenen Lösungsmitteln bestimmten Dissoziation zu. Die NMR‐sowie die Massenspektren werden diskutiert.

On the Chemistry of Fluoroorgano Derivatives of Group 13 Elements. 1 The Reactions of Perfluoroiodoalkanes and Pentafluoroiodobenzene with Triethylindium - Synthesis and Characterization of In(C2H5)2(C6F5) · N(C2H5)3 and In(C2H5)2(i-C3F7) · N(C2H5)3 and Spectroscopic Evidence for Bis(3,3,4,4,4-pentafluorobutyl)indium Iodide

“…However, it must be suggested that In(C 2 H 5 ) 2 R f derivatives and In(C 2 H 5 ) 3 are strong Lewis-acids that completely bond the stoichiometric amounts of N(C 2 H 5 ) 3 . It remains unintelligible that even in the presence of a twofold or threefold excess of N(C 2 H 5 ) 3 no spectroscopic evidence for the quarternary ammonium salt was found.…”

“…The reactions of R f I with In(C 2 H 5 ) 3 with the exception of those of C 2 F 5 I had in common, that one ethyl group was exchanged for one perfluoroorgano group, even if a large excess of the perfluoroiodoalkane was used.…”

“…The highly viscous liquids obtained from reactions of In(C 2 H 5 ) 3 and n-C 3 F 7 I, n-C 4 F 9 I and n-C 6 F 13 I were only analyzed by 19 F-NMR-spectroscopy showing that the acquired products had been formed but were impured with up to 20% of unidentified indium containing derivatives and n-C 6 F 13 H in reactions with n-C 6 F 13 I.…”

“…Examples for successful alkyl-perfluoroalkyl group exchange reactions in main group chemistry are e. g. those of Te(CH 3 ) 2 and R f I to yield Te(CH 3 )R f [6] and of Bi(CH 3 ) 3 and CF 3 I giving mixtures of Bi(CH 3 ) 2 (CF 3 ) and Bi(CH 3 )(CF 3 ) 2 [7].…”

“…The reactions of the higher perfluoroiodoalkanes with Cd(CH 3 ) 2 proceed selectively and quantitatively without any base present [3], whereas reactions with CF 3 I [4] and C 2 F 5 I [5] gave an incomplete exchange or yielded a great number of by-products. However, use of Cd(C 2 H 5 ) as a starting material allowed the synthesis of donor-free Cd(CF 3 ) 2 [4].…”