112532-20-4Relevant articles and documents
Activation of benzene carbon-hydrogen bonds via photolysis or thermolysis of (η5-C5Me5)2Zr(alkyl)H. Isolation of (η5-C5Me5)2Zr(C 6H5)H and its conversion to a complex containing a tetramethylfulvene ligand
Miller, Frederick D.,Sanner, Robert D.
, p. 818 - 825 (2008/10/08)
A new high-yield synthesis of Cp*2ZrH2 (Cp* = η5-C5Me5) is described, and olefin insertion into its Zr-H bond is used to prepare several new Cp*2Zr(alkyl)H complexes. Photolysis or thermolysis of Cp*2Zr(alkyl)H in benzene yields the respective alkane by intramolecular reductive elimination of the cis alkyl and hydride ligands, as well as the benzene C-H bond activation product Cp*2Zr(C6H5)H. Photochemically induced reductive elimination is also observed for Cp*2Zr(C6H5)H and Cp*2ZrH2. Deuterium-labeling experiments show that hydrogen exchange between the hydride and Cp* methyl groups occurs in both Cp*2Zr(H)CH2CH(CH3)2 and Cp*2Zr(C6H5)H. An additional exchange process in Cp*2Zr(C6H5)H involves the hydride ligand and an ortho phenyl hydrogen atom. Thermolysis of Cp*2Zr(C6H5)H in benzene causes quantitative evolution of dihydrogen and reversibly forms the tetramethylfulvene complex Cp*(η6-C5Me4CH2)Zr(C 6H5). Reaction of this compound with iodine produces the Cp* ring substituted phenyl iodide Cp*(η5-C5Me4CH2I)Zr(C 6H5)I. Several of the transformations involving Cp*2Zr(C6H5)H are believed to proceed via β-hydrogen elimination from the phenyl group to yield a benzyne dihydride intermediate.
