Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 462.

The sky-blue titanium derivative [Ti(η7-C7H7)(η5-Cp*)] (‌10‌, Cp′ = Cp*) (‌Scheme 6‌), considered to be the first isolated, stable sandwich complex of titanium, has been prepared by reaction of [TiCp*Cl3] (‌8‌, Cp′ = Cp*) with isopropylmagnesium bromide in the presence of cycloheptatriene.[‌59‌] [Ti(η7-C7H7)(η5-Cp*)] (‌10‌, Cp′ = Cp*) is also obtained by reduction of [TiCp*Cl3] (‌8‌, Cp′ = Cp*) with magnesium.[‌60‌] This reaction with cycloheptatriene, giving complex ‌10‌ (Cp′ = Cp*) as blue crystals, occurs in tetrahydrofuran in the presence of magnesium turnings at room temperature (‌Scheme 6‌). The addition of a catalytic amount of iron(III) chloride increases the yield.[‌61‌] [Ti(Cp*)(cot)] (‌9‌, Cp′ = Cp*) is synthesized similarly (‌Scheme 6‌).[‌57‌] Complex ‌9‌ (Cp′ = Cp*) sublimes above 100°C/0.01 Torr.[‌62‌] Zirconium or hafnium complexes can be obtained in the same way. The sandwich structure has been confirmed by an X-ray diffraction study.

‌Meeeee 8‌ Meeeeeeeeee ee Meeee-Meeeeeee Meeeeeee Meeeeeeee eeee ­Meeeeeeee(eeeeeeeeeeeeeeee)eeeeeeee(MM) Meeeeeeee eee e Meeeee Meeeeeee ee Meeeee, ee eee Meeeeeee ee Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(η8-Meeeeeeeeeeeeeeee)(η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeee(MMM) (‌8‌, Me′ = Me*):[‌88‌]

M eeee ee [MeMe*Me8] (‌8‌, Me′ = Me*; 8.8 e, 8.8 eeee) ee MMM (88 eM) eee eeeee eeeeeeee eeee eeeeeeee ee eee (8.88 e, 88.8 eeee) eee Me eeeeeeee (8.88 e, 88.8 eeee) ee MMM (88 eM) eeee e eeeeee ee 88 eee. Meeee 88 e ee ee, eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee (888°M/88 Meee); eeeee: 8.88 e (88%).

(η8-Meeeeeeeeeeeeeeee)(η8-eeeeeeeeeeeeeeee)eeeeeeee(MMM) (‌8‌, Me′ = Me):[‌88‌]

Mee eeeeeeeee eeeeeeeee eeeee eee eee eeeeeeeeeee ee [Me(Me*)(eee)] (‌8‌, Me′ = Me*) eee eeee eee eee eeeeeeeee ee [Me(Me)(eee)] (‌8‌, Me′ = Me) eeee eee (8.88 e, 88.8 eeee) eee Me eeeeeeee (8.88 e, 88.8 eeee) ee MMM (88 eM) eee [MeMeMe8] (‌8‌, Me′ = Me; 8.88 e, 8.88 eeee) ee MMM (888 eM). Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeee ee eeeeee eeeeeeeeeee; eeeee: 8.88 e (88%).

(η8-Meeeeeeeeeeeeeeee)(η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeee(MM) (‌88‌, Me′ = Me*):[‌88‌]

M eeee ee [MeMe*Me8] (‌8‌, Me′ = Me*; 8.88 e, 8.8 eeee) ee MMM (88 eM) eee eeeee eeeeeeee eeee eeeeeeee ee e eeeeeee ee Me eeeeeeee (8.8 e, 88 eeee), eeeeeeeeeeeeeeee (8.8 eM), eee MMM (88 eM). Meeee 88 e eeeeeeee ee ee, eee eeeeeee eee eeeeeee ee eeeeee eee eee eeeee eeeeeee eee eeeeeeeee ee eeeeeee. Mee eeeeeee eee eeeeee eee eee eee eee, eeeeeeee eeeeeee eee eeeeeeee (888–888°M/8.8 Meee) ee eeee eeee-eeee eeeeeeee; eeeee: 8.88 e (88%); 8M MMM (eeeeeee-e8, δ): 8.88 (e, 8M), 8.88 (e, 88M).

(η8-Meeeeeeeeeeeeeeee)(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) (‌88‌, Me′ = Me):[‌88‌]

Me e eee-eeeeee, eee, 8-M eeeee, eeeeeeee eeee e M8 eeeee, e eeeeeeee-eeeeeeeee eeeeeeee eeeeee, eee e eeeeeeee eeeeeee eee, eeee eeeeee (eeeee eee eeeee eee eeeeeee eeee M8) Me eeeee (88 e, 888 eeee), eeeeeeeee eeeeeeeeeeeeeeee (88 eM, 888 eeee) [888–888°M/888 Meee], eeeee MeMe8 (8 e, 88 eeee) eee eee eeeeeeee MMM (88 eM). Me eeee eeee-eeeeeee eeeeeee eee eeee eeeee, eeee e eeeeee ee 8 e, e eeee ee [MeMeMe8] (‌8‌, Me′ = Me; 88 e, 8.88 eee) ee MMM (888 eM) eeee eee eeeeeeee eeeeee, eeeeeee eeeeeee ee eee eeeeeeee eeeee. {[MeMeMe8] (‌8‌, Me′ = Me) ee eeeeeeeee eee eeeeee eeeeeeee eeee MeMe8 eee [Me(Me)8Me8.].} Meeee eee eeeeeee eee eeee eeeeeee ee ee eeeeeeeee, eee eeeeeeee eeeeeeee eeee eeeeeee eeeee eeeeee. Mee eee-eeeeeeeee eeeeeee eee eeeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeee ee eeeeeeeeeee (888°M/88−8 Meee). Mee eeee eeeeeeeee eee eeeeeeeee, eeeeee eeeeeee eeeee eeee eee, eeeeeeee eeeeeee ee e eeeeeeee-eeeee eeee, eee eeeeeee eeeee ee eeeee; eeeee: 88.8 e (88% eeeee ee eeeeeeee).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88-8, 888.
• 8.Meeeee-Meee, (8888) M 88-8, 888.