NDLI: (2,3-Bis(methylen)bicycIo[2.2.2]octan)zirconocen: Synthese, Struktur und elektrochemische Reduktion/(2,3-Bis(methylene)bicyclo[2.2.2]octane)zirconocene: Synthesis, Structure, and Electrochemical Reduction

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(2,3-Bis(methylen)bicycIo[2.2.2]octan)zirconocen: Synthese, Struktur und elektrochemische Reduktion/(2,3-Bis(methylene)bicyclo[2.2.2]octane)zirconocene: Synthesis, Structure, and Electrochemical Reduction

Content Provider	Scilit
Author	Erker, Gerhard Engel, Klaus Krüger, Carl Tsay, Yi-Hung Samuel, Edmond Vogel, Pierre
Copyright Year	1985
Abstract	Photolysis of diphenylzirconocene and 2,3-bis(methylene)bicyclo[2.2.2]octane in toluene at -25 °C yields biphenyl and (2,3-bis(methylene)bicyclo[2.2.2]octane)zirconocene (lg) (67.5% isolated yield).1g exhibits dynamic NMR spectra indicating rapid alternation of diene faces coordinated to zirconium (ring-flip mechanism). This degenerate intramolecular rearrangement is characterized by an extremely low activation barrier (⊿G^≠ _-131°C = 7.1 ± 0.3 kcal/mol). 1g crystallizes in space group P1̄with a = 7.215(1) Å, b = 9.654(1) Å, c = 11.831(1) Å, α = 94.97(1)°, β = 91.81(1)°, and γ = 103.22(1)°. The X-ray structure determination reveals a pronounced metal alkyl character of the (diene)ZrCp₂ moiety. Accordingly, 1g is easily reduced electrochemically to give a Zr(III) radical anion (7) observed by esr (g = 1.990; a(H) = 2.976 G; a(Zr) = 18.36 G).
Related Links	http://www.degruyter.com/downloadpdf/j/znb.1985.40.issue-2/znb-1985-0203/znb-1985-0203.xml
Ending Page	157
Page Count	8
Starting Page	150
ISSN	09320776
e-ISSN	18657117
DOI	10.1515/znb-1985-0203
Journal	Zeitschrift für Naturforschung B
Issue Number	2
Volume Number	40
Language	English
Publisher	Walter de Gruyter GmbH
Publisher Date	1985-02-01
Access Restriction	Open
Subject Keyword	Zeitschrift Für Naturforschung B Inorganic Chemistry (s-cis-conjugated Diene)zirconocene Complexes Diene Metallocene Automerization Diene Zirconocene Electrochemical Reduction Journal: Zeitschrift für Naturforschung B, Vol- 40
Content Type	Text
Resource Type	Article
Subject	Chemistry

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