106017-41-8Relevant articles and documents
Reactions of (acenaphthylene)chromium tricarbonyl with organolithium compounds, trifluoroacetic acid, and organotin hydrides
Kirss, Rein U.,Treichel, Paul M.,Haller, Kenneth J.
, p. 242 - 249 (2008/10/08)
The reactivity of (acenaphthylene)chromium tricarbonyl (I) has been studied. Lithiation at the 3-position of the ligand is facile, and the resulting species was used, in situ, in further reactions with D2O, CH3I, (CH3)3SiCl, BrCH2CH2Br, CH3CHO, and C6H5CHO to provide derivatives of I substituted in the 3-position. Reactions of I with lithium salts of four tertiary carbanions (LiR, R = C(CH3)2CN, C(CH3)2CO2C2H5, C(CH3)2CON(C2H5)2, and C(CH3)3) result in addition of the carbanion to the coordinated hydrocarbon; subsequent oxidation using I2 yields monosubstituted acenaphthylenes RC12H7 and a coupled product, R2C24H12. The former product occurs as a mixture in which the 3-substituted isomer is the predominant species (>90%). Crystal structure studies on 3-C12H7C(CH3)2CO2C 2H5 and on C24H12[C(CH3)2CON(C 2H5)2]2 are reported. Butyllithium adds to the double bond in I, and, after protonation one can isolate Cr-(CO)3(η-1-C4H9C12H 7). Free radical addition of trimethyltin hydride to this double bond is also seen, forming Cr(CO)3[η-1-(CH3)3SnC12H 7]. When dissolved in neat trifluoroacetic acid, I undergoes a unique oxidative coupling reaction through the hydrocarbon giving a product Cr(CO)3(η-C24H18). A number of anticipated reactions of I were found not to occur.
