82397-21-5Relevant academic research and scientific papers
INDENYL AND FLUORENYL TRANSITION METAL COMPLEXES. VII. INNERSPHERE RICOCHET REARRANGEMENTS ON ALKYLATION OF η5-INDENYL- AND η5-FLUORENYLTRICARBONYLCHROMATE ANIONS
Nesmeyanov, A. N.,Ustynyuk, N. A.,Novikova, L. N.,Andrianov, V. G.,Struchkov, Yu. T.
, p. 239 - 250 (1982)
Alkylation of K5-C9H7Cr(CO)3> (Xa) with CH3I and C6H5CH2Br leads to o-alkyl derivatives of η5-C9H7Cr(CO)3Alk type.These complexes undergo innersphere ricochet rearrangement, with the alkyl group being shifted to the endo position at C(1) and the chromium tricarbonyl group shifted to the benzene nucleus.The structure of the product of such a rearrangement in the case of η5-C9H7(CO)3CrCH2C6H5, i.e. (1-benzyl-3a,4-7,7a-η6-indene)chromium tricarbonyl (XVIII), is established by a low temperature X-ray study, indicating an endo position for the benzyl radical.On alkylation of equilibrium tautomeric mixtures of η5- and η6-fluorenyl-chromium tricarbonyl anions XIa XIb under similar conditions, the η5-anion (Xa) yields a ?-alkyl derivative, which is rearranged to (9-endo-alkyl-1-4,4a,9a-η6-fluorene)chromium tricarbonyl.Electrophilic attack of the η6-anion (XIb) takes place on the outer side at C(9) and leads to a corresponding 9-exo-alkyl derivative.
