Synthesis and Chemistry of CF3C6F4OC6F4 Group 14/16 Derivatives

Krumm, Burkhard; Kirchmeier, Robert L.; Shreeve, Jean’ne M.

doi:10.1021/ic970528d

Cited by 4 publications

(2 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5] Very recently, in situ by lithiation of C 6 F 5 H, respectively 4-(4Јa high-yield synthesis of a new diselane [4-(4Ј-CF 3 C 6 F 4 O)C 6 F 4 H, [12] with n-butyllithium (Scheme 1). [6] This method is extended in this report to the synthesis of the known C 6 F 5 SeSeC 6 F 5 . [6] This method is extended in this report to the synthesis of the known C 6 F 5 SeSeC 6 F 5 .…”

Section: Resultsmentioning

confidence: 90%

Synthesis, Chemistry, and Characterization of Perfluoroaromatic Selenium Derivatives

Klapötke

Krumm

Polborn

1999

Eur. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The reaction of perfluoroaryllithium RC6F4Li, where R = F or 4‐CF3C6F4O, respectively, with selenium gives the known diselanes (RC6F4Se)2 (1a, 1b). Redox reactions of 1 with hydrogen peroxide result in the formation of the seleninic acids RC6F4SeOOH which crystallize as hydrates (2a, 2b); with mercury give the bis(arylseleno)mercuries (RC6F4Se)2Hg (3a, 3b); with sulfuryl chloride or bromine give the selenenyl chlorides (4a, 4b) or selenenyl bromides (5a, 5b). Selenenyl chlorides (4a, 4b) react with a variety of trimethylsilyl reagents Me3SiX (X = Br, CN, NMe2, NEt2) to form 5a, 5b; selenocyanates RC6F4SeCN (6a, 6b); selenenyl amides RC6F4SeNMe2 (7a, 7b) and RC6F4SeNEt2 (8a, 8b). A new synthetic route to diorgano selanes is developed by reaction of 4a, 4b with perfluoroaryllithium to give the symmetric (RC6F4)2Se (9a, 9b). All derivatives are thoroughly characterized and in addition the molecular structures of 2a, 6a, and 9a are established by X‐ray crystallography.

show abstract

Section: Resultsmentioning

confidence: 90%

Synthesis, Chemistry, and Characterization of Perfluoroaromatic Selenium Derivatives

Klapötke

Krumm

Polborn

1999

Eur. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The calculated total energies (Table 2) can be used to predict theoretically the heat of reactions (4) and (5). The heats of reactions (4) and (5) (DU el ) were calculated (Table 3), which, after correction [11] for zeropoint energies (zpe, Table 2; DU vib ), differences in rotational (DU rot = RT) and translational (DU tr = 0 RT) degrees of freedom, and the work term (pDV = 0 RT), were converted into the DH°values at room temperature (enthalpy value) ( Table 4).…”

Section: Calculationsmentioning

confidence: 99%

The Reactivity of CF3C6F4OC6F4Li towards Halogens and Cyanogen Halides

Klapötke¹,

Krumm²,

Polborn³

2000

Z. anorg. allg. Chem.

Self Cite

View full text Add to dashboard Cite

The reaction of 4-(4'-tri¯uoromethyl-tetra¯uorophenoxy)-tetra¯uorophenyllithium (R F Li, 1) with halogens, dicyanogen, cyanogen halides, and xenon di¯uoride was examined. The corresponding halogenated aromatics R F Cl (2), R F Br (3) and R F I (4) were formed upon reaction with chlorine, bromine, and iodine. Essentially the same products were isolated in the reaction of 1 with cyanogen chloride, bromide, and iodide, respectively. The nitrile R F CN (5) was obtained from the reaction of 1 with dicyanogen only as a minor product. The reaction of 1 with XeF 2 resulted in the isolation of R F CH(CH 3 )CH 2 CH 3 (6). All products were identi®ed and characterized by analytical and spectroscopic methods. In addition the molecular structures of 2, 3, and 4 have been determined by X-ray crystallography. The reaction enthalpies for the gas phase reactions of penta¯uorophenyllithium, C 6 F 5 Li, as a model for 1, with XCN (X = F, Cl, Br, I) were calculated. Das Chemische Verhalten von CF 3 C 6 F 4 OC 6 F 4 Li gegenu È ber Halogenen und HalogencyanenInhaltsu È bersicht. Die Reaktion von 4-(4'-Tri¯uormethyl-te-tra¯uorphenoxy)-tetra¯uorphenyllithium (R F Li, 1) mit Halogenen, Halogencyanen, Dicyan und Xenondi¯uorid wurde untersucht. Die entsprechenden halogenierten Aromaten R F Cl (2), R F Br (3) und R F I (4) entstanden bei der Umsetzung mit Chlor, Brom und Iod. Die gleichen Produkte wurden bei der Reaktion von 1 mit Chlorcyan, Bromcyan und Iodcyan gebildet und isoliert. Das Nitril R F CN (5) wurde erhalten bei der Reaktion von 1 mit Dicyan nur als Nebenprodukt. Die Reaktion von 1 mit XeF 2 fuÈ hrte zu der Isolierung von R F CH(CH 3 )CH 2 CH 3 (6). Alle Produkte wurden mittels analytischer und spektroskopischer Methoden identi®ziert und charakterisiert. Die MolekuÈ lstrukturen von 2, 3 und 4 wurden bestimmt. Die Reaktionsenthalpien fuÈ r die Reaktionen in der Gasphase von Penta¯uorphenyllithium, C 6 F 5 Li als ein Modell fuÈ r 1, mit XCN (X = F, Cl, Br, I) wurden berechnet.

show abstract