Synthesis, structure, and reactivity of bis(1,2,4-tri-t-butlcyclopentadienyl) complexes of cerium
Evan L. Werkema, University of California, Berkeley (Degree granting institution)
The sterically demanding 1,2,4-tri-t-butylcyclopentadienyl ligand (1,2,4-(Me 3C)3C5H2, hereafter Cp') has been used to prepare monomeric cerium metallocenes, Cp '2CeX (X = Cl, I, OSO2CF3), which are used to synthesize the benzyl, Cp'2CeCH 2C6H5. The benzyl is a useful starting material for preparing other complexes in the Cp'2CeZ system (Z = BF4, F, NH2, C6H5, H). X-ray crystal structures of Cp'2CeOSO 2CF3, Cp'2CeF, Cp '2CeCH2C6H5, and Cp'2CeH are presented. The benzyl slowly decomposes in solution to toluene and a metallacycle, [Cp'][(Me 3C)2C5H2(CMe2CH2)]Ce. The ring CMe3 groups of both the metallacycle and the hydride, Cp'2CeH, can be fully deuterated by prolonged exposure to C6D6, providing a useful labeling tool in mechanistic studies
Thesis, Dissertation, English, 2005