The reaction of Cp2Ti(CH2Ph)2 (5) with Ag[BPh4] in CD3CN yields bibenzyl, Cp2-TiIV{N==C(CH3)(CH2Ph)}(NCCH3)+ (6a,b), and Cp2TF(NCCH3)2+ (7) as the BPhf salts.Recrystallization of 7 from hot THF yields Cp2Tim(THF)(NCCH3)+ (8), which has been characterized by X-ray crystallography. Labeling studies show that reaction of 5 with Ag- [BPh4] proceeds via a stepwise mechanism, involving initial generation of the reactive cationic monobenzyl species Cp2Ti(CH2Ph)(NCCH3)+ ( 12) followed by competitive insertion to yield 6a,b or Ti-benzyl bond homolysis to yield 7. Intermediate 12 has also been generated by (i) one-electron oxidation of Cp2Tim(CH2Ph) with AgBPht, (ii) reaction of 5 with Cp'2Fe+ (Cp' = C5H4Me), (iii) protonolysis of 5 with HNMe3\ and (iv) reaction of Cp2Ti(CH2Ph)(Cl) with NaBPht in CH3CN. The reaction of 5 with either Cp'2Fe+ or HNMe3+ in THF yields the cationic Ti(III) complex Cp2Ti(THF)2+ ( 19), most likely via an intermediate Cp2Ti( CH2Ph)-(THF)+ species. The metastable, base-free ion pair Cp2Ti(CH2Ph)(CBnH12) (22) has been observed spectroscopically. Complex 22 reacts with CD3CN to form 6a,b-de as the CBUH12" salts. The chemistry of these reactive Cp2Ti(CH2Ph)(L)+ species is contrasted with that of related group 4 metal complexes.
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