Cationic Cyclopentadienyl Phenylenediamido Titanium Species Generated by Reaction of TiCp<sup>R</sup>[1,2-C<sub>6</sub>H<sub>4</sub>(NCH<sub>2</sub><i>t-</i>Bu)<sub>2</sub>]R (Cp<sup>R</sup> = η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>, η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>; R = CH<sub>3</sub>, CH<sub>2</sub>Ph) with B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>. X-ray Molecular Structure of Ti(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)[1,2-C<sub>6</sub>H<sub>4</sub>(NCH<sub>2</sub><i>t-</i>Bu)<sub>2</sub>][μ-MeB(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>]<sup>†</sup>
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The reaction of TiCpR[1,2-C6H4(NNp)2]R with the Lewis acid B(C6F5)3 in noncoordinating solvent affords the new zwitterionic species TiCpR[1,2-C6H4(NNp)2)][μ-RB(C6F5)3]. When the reaction is performed in dichloromethane, the [μ-RB(C6F5)3]- anion is displaced by solvent molecules, giving ionic products in which the anion is not coordinated. The cyclopentadienyl zwitterionic complexes TiCp[1,2-C6H4(NNp)2)[μ-RB(C6F5)3] decompose via ligand scrambling between boron and titanium to give the neutral titanium complex TiCp[1,2-C6H4(NNp)2](C6F5) along with the byproduct RB(C6F5)2. In contrast, the pentamethylcyclopentadienyl analogues TiCp*[1,2-C6H4(NNp)2][μ-RB(C6F5)3] evolve through C−H activation to yield an unresolved mixture of compounds. The molecular structure of TiCp*[1,2-C6H4(NNp)2][μ-MeB(C6F5)3] has been determined by X-ray diffraction methods.
