Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 560.

The thermolysis of [Ti(Cp)2(Ph)2] (‌252‌) is thought to involve a benzyne intermediate ‌253‌ (‌Scheme 125‌). In the absence of suitable donor ligands, [Ti(Cp)2(η2-aryne)] species have only a fleeting existence. The thermolysis of [Ti(Cp)2(Ph)2] (‌252‌) and following reaction with methylenetriphenylphosphorane proceeds either by C—H activation to give ylide complex ‌254‌, or by methylene transfer to give titanacyclobutabenzene complex ‌230‌ (‌Scheme 125‌).[‌370‌] The crystal structure of ‌254‌ confirms that the adopted conformation maximizes the π-interaction between titanium and the ylide carbon atom.[‌345‌] The compound does not react with ketones. Reactions of the benzyne intermediate ‌253‌ with metal–carbonyl complexes lead to titanium-substituted Fischer carbene complexes such as ‌255‌ (‌Scheme 125‌). The zirconium analogues are similarly accessible.[‌371‌]

‌Meeeee 888‌ Meeeeeeee eee Meeeeeeeee ee Meeeeeeeeeeeeee Meeeeeeee[‌888‌–‌888‌]

Mee eeeeeeeeeee ee [Me(Me)8(η8-MeM8M8)8] ee eeeeeee ee 88°M eeeee e eeeeeee eeeeeee ‌888‌ ee e eeeeee eeeeeeee eeeeeeeeeeee, eeeee eeeeeeeeee eeeeee ee eeeeeeee eeee e eeeeee M—M eeee ee eeee ‌888‌, e eeeeeee eeee eeeee eee, ee eeeeee eeeeeeeeeeee eeeee (‌Meeeee 888‌).[‌888‌]

Meeeeeeeeeee Meeeeeeee

[μ-Meeeeeee-8,8-eeeeeeeee]eee(η8-eeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeeeeee(MM)eeeeeeee(MM) (‌888‌, M = Me):[‌888‌]

M eeeeeee ee [Me(Me)8(Me)8] (‌888‌; 88.8 e, 88.8 eeee) eee Me(MM)8 (8.8 e, 88.8 eeee) eee eeeeeeeeeee ee eeeeeee (8888 eM) eee 88 e ee 88°M. Mee eee eeeeeee eee eeeeeeee, eee eee eeeeeeeee eeee eee eeee ee eee eee eeeeeeeeeee eee 88 e. Mee eeeeeeeeeee eee eeeeeee ee eeeeeeeeee. Mee eeeeeee [eeeee: 8.8 e (88%)] eeeeeeeee eeee Me(MM)8, eeee ee eeeee eee eeeeeee ee eeeeee eeeeeeeeeee ee 88°M; 8M MMM (MM8Me8, δ): 8.88 (e, 8M, M8), 8.88, 8.88 (e, 8M, M8/8), 8.88 (e, 88M, Me), ee. 8.8 (8M, eeeeee ee eeeeeee); 88M MMM (MM8Me8, 88°M, δ): 888.8 (e, eeeeeee M), 888.8 [e, 8M, Me(MM)], 888.8 [e, 8M, Me(MM)], 888.8 (e, M8), 888.8 (e, 8MMM = 888 Me, M8), 888.8 (e, 8MMM = 888 Me, M8), 888.8 (e, 8MMM = 888 Me, M8), 888.8 (e, 8MMM = 888 Me, M8), 888.8 (e, 8MMM = 888 Me, Me).

References

Meeeeee Meeeeeeeeee

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