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2.10.3.1 Method 1: Salt Elimination Reactions between Cyclopentadienyllithium Compounds and Titanium(IV) Chloride

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032468.

Bis(cyclopentadienyl)titanium derivatives can be prepared by the reaction of titanium(IV) chloride with the lithium salts of the less sterically hindered cyclopentadienides. Mixed-ligand dichlorobis(η5-cyclopentadienyl)titanium(IV) complexes are available by the reaction of trichloro(η5-cyclopentadienyl)titanium(IV) compounds, such as trichloro(η5-cyclopentadienyl)titanium(IV) (79) or [Ti(Cp*)Cl3] (6), with the lithium salt of a substituted cyclopentadienide. The preparation of [Ti(Cp)(Cp)Cl2] complexes often results in a statistical mixture of [Ti(Cp)2Cl2], [Ti(Cp)(Cp)Cl2], and [Ti(Cp)2Cl2]. This problem is partially circumvented by slow addition of the reagents. Typically, the synthesis of mixed-ligand compounds results in the formation of less than 10% [Ti(Cp)2Cl2] (78). Methylene-, silylene-, germylene-, phosphinediyl-, and arsinediyl-bridged ansa-titanocene complexes 33 can be synthesized from lithium salts (Scheme 13).[‌102‌] Brintzinger has demonstrated that in dimethylsilyl­ene-bridged metallocenes the rac-isomer predominates if the cyclopentadienyl rings bear an additional substituent, R1, at the 2-position (R1=iPr, Me).[‌87‌] The (diphenylphosphino)cyclopentadienyl- (34) and [(diphenylphosphino)ethyl]cyclopentadienyl complexes 35 (Scheme 13), have also been synthesized by the reaction of their respective lithium salts.[‌103‌] Chiral, mixed-cyclopentadienyl complexes 36[‌104‌] and 37[‌105‌] are also prepared from the reaction between titanium(IV) chloride and the appropriate cyclopentadienyllithium salts (Schemes 14 and 15).

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Meeeee 88 Meeeeeeeeee ee Meeeeeee[eeeeeeeeeeeeee(8-η8-8-eeee-eeeeeeeeeeeeeeeeeeeee)(8-η8-8-eeee-eeeeeeeeeeee)]eeeeeeee(MM)[‌888‌]

Meeeee eeee-eeeeeeeeeee eeeeeeeee eeee eeeeee eeeeee ee eeeeeeeee ee eeeeeeeeee eeeeeeeee. Meeee eeeeeee-eeeeeeeeee ee eeee-eeeeeeeeeee eeeeeeeee eeeeee eeeee eeee eeee 88% ee e eeeeeeeeee eeeeeeeeee, eee eeeeeee eeeeeeeeee eeeeeeee ee e eeeeeeee-eeeeeee eeeeeeeeeee eeeeeee 88 eee eeee eeeeeeee ee eeee eeeeeeeeeee eeee-eeeeeeeeee eeeeeeeee eeeeeee 8,8-ee(8-eeeeeeee) (MMMMM) eeeeeee eeeeeeeeee eeeeeeeeeeeeee (Meeeee 88). Mee eeeeeee, eee eeeeeeee-eeeeeee eeeeeee eee-88 eeeee, eee 8,8-ee(8-eeeeeeeeeee) eeeeeee (M)-88, ee (M)-88, eeeee, ee eee eeeeeeee ee eeeeeeeeeeee, ee ee eeeeeeeee eeeeeeeeee eeeeeeee eee eeeee eeeeeeeeeeeee; eee eeeeeee, eeeeeeeeeee 88 ee eeeeee ee 88% ee eeee eeeeeeeeeeeeee 88 (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeee eee Meeeeeeee Meeeeeee ee ee Meeeeeeeeeeeeeee Meee eeee-Meeeeeeeee Meeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeee(η8-eeeeeeeeeeeeeeeeeeeeee)eeeeeeee(MM); Meeeeee Meeeeeeee:[‌888‌]

M eeeeee ee eeeeeeeeeeeeeeeeeeeeeeeeeeeee (8.8e, 888eeee) ee Me8M eee eeeeee eeeee ee e eeee ee MeMe8 (8.8eM, 88eeee) ee Me8M eeeee eeeee ee 8°M. Meeee eee eeee eee eeee eeeeeee eee 88eee, eee eeeeeee eee eeeeeee ee eeeee ee eeeee e eeeeeee-eeeeee eeeeee. Mee eeeeee eeee eeeeeee eeee e eeee eee eeeeee eeee 8M ee MMe eeeee eee eeeeeeee eeee eeeeeeeee. Mee eeeeeee eee eeee eeeeee eeee MeMM (8×8eM) eee Me8M (8×8eM), eee eeeeeeeeeeeeee (eee eeeeeee); eeeee: 8.8e (88%); 8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M).

Meeeeeee(η8-eeeeeeeeeeeeeeee)[η8-(eeeeeeeeeeeeee)eeeeeeeeeeeeeeee]eeeeeeee(MM); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeeeeee ee (eeeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeeeeee (8.88e, 8.8eeee) ee MMM (88eM) eee eeeeee eeeee eeeeeeee ee eeeeeee ee e eeeeeee eeee ee [MeMeMe8] (88; 8.88e, 8.8eeee) ee MMM (88eM) eeeee eeeee ee ee. Meeee eee eeeeeeee eee eeeeeeee, eee eeeeeeeee eee eeee eee eeeeeee eee 88eee. Mee eeeeeee eee eeeeeee ee eeeee ee eeeee e eeeeeee-eeeeee eeeeee. Mee eeeeee eeee eeeeeee eeee e eeee eee eeeeee eeee 8M ee MMe eeeee eee eeeeeeee eeee eeeeeeeee. Mee eeeeeee eee eeeeee eeeeeee eeeee eeee MeMM eee Me8M, eee eeee eeeeeeeeeeeeee (eee MMMe8/eeeeeee) ee eeeee eeee eee eeeeeee; eeeee: 8.8e (88%); 8M MMM (MMMe8, δ): 8.88 (e, M=8Me, 8M), 8.88 (e, M=8Me, 8M), 8.88 (e, 8M), 8.88 (e, 8M). Me [Me(Me)8Me8] (88) eee eeeeeeee ee 8M MMM.

eee- eee eeee-Meeeeeee[eeeeeeeeeee(8-η8-eeeeeee)]eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee-eeeeee eeeee, eeeeeeee eeee e eeeeeeee eeeeee, e eeeeee eeeeeeeee, eee e eeeeeeee eeeeeee eee, MMM (888eM) eee eeeeee ee 88°M eee MeMe8 (8.8eM, 88eeee) eee eeeee. Mee eeeeeeeee eeeeee eeeeeeeeee eee eeeeee ee eeeeee eeee eeeeeeee eeeee M8, eee e eeee ee [eeeeeeeeeee(eeeeeee)]eeeeeeeee (88eeee) eee eeeee eee ee eeee eeee eee eeeeeeee eeeeee; eee eeeeeeeee eeeeeee eee eeeeeee eee eeeee 88eee, eeee eeeeee ee ee. Meeeeee MMe eee eeeeeee eeeeeee eee eeeeeee eee eeeee 88e, eeee eee eeeeeee eee eeeeeee ee eeeee. Mee eeeeeeeeee eeeeeeeeeeee eeeee eeee eeeeeeeee eeeeeee eeeee eee eeeeeeeeee. Mee eeeeeee eeeeeeee eeeee eeeeeee ee eeeeeee eee eeeeee ee e Müeeeee eeeeee eeee eeeeeee eeeeeeee ee Me8M eeeee eee eeeeeeee eee eeeeeeeeeee eeeeeeeee. Mee eeeeeee eee eeee eeeeee eeee 88% ee MMe, M8M, MeMM, eee Me8M. Meeee ee eeeee eeeeee, e eeeeeee ee eee- eee eeee-88 eee eeeeeeee ee e eeee eeeeeeee-eeeee eeeeee; eeeee: 8.8e (88%). Mee eee-eeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee); 8M MMM (MMMe8, δ): 8.888.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.888.88 (e, 8M).

eee-Meeeeeee[eeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeeee)(8-η8-eeeeeee)]-eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee 8-(8-eeeeeee)-8-(8,8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeee (8e, 8.8eeee) ee Me8M (88eM) eee eeeeee ee 8°M, 8.8M MeMe ee Me8M (88eeee, 8eM) eee eeeee eeeeeeee, eee eee eeeeeee eee eeeeeee eee 88e ee ee. Mee eeeee eeeee eeeeeee eee eeeeee eeeeeee eeeee eeee eeeeeee (88eM), eeeeeeeee ee eeeeeee/Me8M (8:8, 88eM), eee eeeeee ee 88°M. M eeee ee MeMe88MMM (8.88e, 8.8eeee) ee Me8M (88eM) eee eeeee eeeeeeee eee eee eeeeeee eee eeeeeee ee eeeee ee ee eee 88e, eeeee eeeee ee eee eeeeeeee, eee eee eeeeeee eee eeeeeee eeee eee eeeeeeee ee eeee eeeee eeeeeee 88; eeeee: 88%. Meee eee eeeeeeeeeeeeee (eeeeeee/eeeeeee). Mee 8M eee 88M MMM eeeeeee eeeeeeeee eeee eeee eee ee eee eee eeeeeeee eeeeeeeeeeeeee eeeee eee eeeeeee. Meee eee eeeeeeee ee ee 88M ee eee eeeee ee eeeeee eeeeeeeeeeeeee.[‌888‌] Mee eeeeee-eeeeeee eeeeeeeee eeeeeeeeeeeee ee eee eeeeeeee eeeeeeeeee eeeeeeeee eeee eeeeeeeeee.[‌888‌] 8M MMM (MMMe8, δ): 8.888.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, M=8.8Me, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M); 88M MMM (MMMe8, δ): 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 888.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8, 88.8.

Meeeeeee[eeeeeeeeeeeeee(8-η8-8-eeee-eeeeeeeeeeeeeeeeeeeee)(8-η8-8-eeee-eeeeeeeeeeee)]-eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌888‌]

8-(8-eeee-Meeeeeeeeeeeeeeeeeeee)-8-(8-eeee-eeeeeeeeeeee)eeeeeee (88.8e, 88eeee) eee eeeeeeeee ee eee MMM (888eM), eee eee eeee eee eeeeee ee 88°M. 8.8M MeMe ee eeeeeee (88.8eM, 88eeee) eee eeeee eeeeeeee eeee 88eee. Mee eeeeeeeee eee eeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 8e. Mee eeeeeee eee eeeeeee, eee eee eeeeeee eee eeeeeeeee ee MM8Me8 (888eM) ee 88°M. Mee eeeeee eeee eee eeeee ee e eeeeeeeeee ee MeMe88MMM (8.88e, 88eeee) ee MM8Me8 ee 88°M. Mee eeeeeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 88e. Mee eeeeeee eee eeeeeee, eee eee eeeeeee eee eeeeeeeee eeeeeee eeeee eeee eeeeeeee ee eee eeeeeee (888eM); eee eeeeeee eeeee eeee eeeeeeeee eeee eee eeeeeeee ee eeeeeeeeee. Meeeeeeeeeeee, eeeeeeee ee eeeeeee ee 88°M eeee e eeeee eeeeee; eeeee-88 eee eeeeeeee ee eeeeeeeeeeeeeeeee (eeeeeee);8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M).

Meeeeeeeee Meeeeeeeeeeee Meeeeeeee; Meeeeee Meeeeeeee:[‌888‌]

Me e eee Meeeeee eeeee, eeee-eeeeeee (M)-88 (8.8ee, 88 μeee) eee eeeeeeeee ee eeeeeee (88eM) eeeee ee eeeee eeeeeeeeee ee ee. 8.88M MeMe ee eeeeeee (8.88eM, 88 μeee) eee eeeee eeeeeeee. Mee eeeee eeeeeee eeeeeee ee e eeeee eeeee-eeeee. Meeee 8eee, e eeee ee eee eeeee (88eeee, 8888 eeeee) ee eeeeeee (88eM) eee eeeee. Mee eeeeeeeee eeee eee eeeeeeeeeee eeeee eeeee ee e Meee eeee-eeeeeeee eeeeeeeee, eeeeeee eeee M8 eee (88.888+%, 8.8 × 888 Me), eee eeeeeee ee eeee eee 88e ee 88°M. Meeee eeeeeee ee ee, eee eeeeee eee eeeeeeeee eeeeee eee eeeeee. Mee eeeeeee eee eeeeeee ee eeeee eeee eee eeeee eeeeeee, eee eee eeeee eeeeeeee eee eeeeeeee ee Meeeeeeee eeeeeeeeeeee. Mee eeeeeeeeeeee eeeeee ee eee eeeeee eee eeeeeeeeee ee eeeeeeeeeeeeeeeeeee eee eeeeeeeeee MM eeeeeeee ee e MM-M eeeeee.

References


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