%0 Generic %A Hoyt, Helen M. %A Michael, Forrest E. %A Bergman, Robert G. %D 2004 %T C−H Bond Activation of Hydrocarbons by an Imidozirconocene Complex %U https://acs.figshare.com/articles/dataset/C_H_Bond_Activation_of_Hydrocarbons_by_an_Imidozirconocene_Complex/3351277 %R 10.1021/ja0385944.s001 %2 https://ndownloader.figshare.com/files/5190589 %K Mechanistic experiments support %K Lewis base %K intramolecular elimination %K imidometallocene systems %K butyl amide %K activation %K Imidozirconocene Complex Monomeric imidozirconocene complexes %K type Cp 2 %K bond %X Monomeric imidozirconocene complexes of the type Cp2(L)ZrNCMe3 (Cp = cyclopentadienyl, L = Lewis base) have been shown to activate the carbon−hydrogen bonds of benzene, but not the C−H bonds of saturated hydrocarbons. To our knowledge, this singularly important class of C−H activation reactions has heretofore not been observed in imidometallocene systems. The MNR bond formed on heating the racemic ethylenebis(tetrahydro)indenyl methyl tert-butyl amide complex, however, cleanly and quantitatively activates a wide range of n-alkane, alkene, and arene C−H bonds. Mechanistic experiments support the proposal of intramolecular elimination of methane followed by a concerted addition of the hydrocarbon C−H bond. Products formed by activation of sp2 C−H bonds are generally more thermodynamically stable than those formed by activation of sp3 C−H bonds, and those resulting from reaction at primary C−H bonds are preferred over secondary sp3 C−H activation products. There is also evidence that thermodynamic selectivity among C−H bonds is sterically rather than electronically controlled. %I ACS Publications