Comparison between a Diarylferrocenylmethylium Ion and Its Isolobal Cobalt Species: Similarities and Differences

Autor:	Rolf Gleiter, Holger Schimanke, Sandro Johannes Silverio, Michael Büchner, Gottfried Huttner
Rok vydání:	1996
Předmět:	Chemistry Organic Chemistry chemistry.chemical_element Isolobal principle Ether Carbocation Photochemistry Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Cyclopentadienyl complex Bromide Moiety Physical and Theoretical Chemistry Cobalt Fulvene
Zdroj:	Organometallics. 15:5635-5640
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om960694d
Popis:	Reaction of {(1,2,8,9-η)-tricyclo[7.5.0.01,7]tetradeca-1,8-diene}{η5-(methoxycarbonyl)cyclopentadienyl}cobalt (9) with either 2 mol of arylmagnesium bromide or aryllithium and subsequent hydrolysis yields the alcohols {(1,2,8,9-η)tricyclo[7.5.0.01,7]tetradeca-1,8-diene}{η5-(diarylhydroxymethyl)cyclopentadienyl}cobalt (13a−c). The treatment of the yellow colored alcohols 13a−c with HBF4 in ether affords the tetrafluoroborates of the violet colored carbocations 14a−c. Investigations of single crystals of 14b by means of the X-ray technique show a displacement of the C1−Cexo bond by α = 10.8° toward the metal and a pronounced bond alternation in the fulvene moiety. The bending of C1−Cexo is considerably larger than in the corresponding alcohol 13b (α = 2.5°). The interaction between the exo-carbon and the metal in 14b is further substantiated by comparison of the 13C-NMR chemical shift of 14b with 13b (Δδ = −65 ppm). The comparison of the data obtained for 14b with those of diphenylferrocenylcarbenium ion 1b...
Databáze:	OpenAIRE
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