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Stereoisomeric 2,5-Dimethyl-2,3:4,5-dioxidohexanes as the Main Products of the Pyrolysis of Polymeric 2,5-Dimethyl-2,4-hexadiene Peroxide

✍ Scribed by Dr. G. Bernhardt; Prof. Dr. F. Korte

Publisher: John Wiley and Sons
Year: 1965
Tongue: English
Weight: 237 KB
Volume: 4
Category: Article
ISSN: 0044-8249
DOI: 10.1002/anie.196501492

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✦ Synopsis

The [Co(PF3)4]0 anion can be precipitated from aqueous solutions with voluminous cations. During the conversion of HCo(PF3)d into [Co(PF3)4]0, a bathochroniic shift of the P-F valence vibrations is observed which is probably due to a reduction in the double-bond character of the P-F bond.

At PF3-pressures above 200 atm and temperatures above 200 OC, tungsten hexachloride reacts with copper powder as halogen acceptor to form colorless crystals of hexakis(trifluorophosphine) tungsten(0). W(PF3)6 completes the series of hexakis(trifluorophosphine) complexes of the chromium group [4]. The new compound, m.p. 214'C, is completely analogous to the corresponding chromium and molybdenum complexes. It sublimes rapidly in a high vacuum at 4OoC and decomposes only above 32OoC with formation of a tungsten mirror. Its infrared spectrum has P-F valence vibrations at 914 (vs) and 852 (s) cm-1 [3] and indicates an octahedral structure of the diamagnetic complex.

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