Non-Redox Assisted Oxygen-Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp(2)Ti(eta-OOBu)L], L = Cl, OTf, Br, OEt(2), Et(3)P.

ABSTRACT: The titanium(IV) alkylperoxide complex Cp(2)Ti(OO(t)Bu)Cl (1) is formed on treatment of Cp(2)TiCl(2) with NaOO(t)Bu in THF at -20 degrees C. Treatment of 1 with AgOTf at -20 degrees C gives the triflate complex Cp(2)Ti(OO(t)Bu)OTf (2), which is rapidly converted to the bromide Cp(2)Ti(OO(t)Bu)Br (3) on addition of (n)Bu(4)NBr. The X-ray crystal structures of 1 and 3 both show eta(1)-OO(t)Bu ligands. Complex 2 is stable only below -20 degrees C; (1)H, (13)C, and (19)F NMR spectra suggest that it also contains an eta(1)-OO(t)Bu ligand. Removal of the chloride from 1 with [Ag(Et(2)O)(2)]BAr'(4) (Ar' = 3,5-(CF(3))(2)C(6)H(3))) yields the etherate complex [Cp(2)Ti(OO(t)Bu)(OEt(2))]BAr'(4) (4). Again, coordination of a fourth ligand to the Ti center indicates an eta(1)-OO(t)Bu ligand in 4. These

SUBMITTER: Dipasquale AG 

PROVIDER: S-EPMC2519019 | biostudies-literature | 2006

REPOSITORIES: biostudies-literature