0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via Method 2: Titanium(III) Complexes by Reduction of Titanium(IV) Complexes by Lithium Nitride

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032502.

In coordinating solvents, lithium nitride acts as a reducing reagent, liberating dinitrogen; for example, titanium(IV) chloride is reduced by lithium nitride to Li[TiCl4]4THF, [Ti(Cp)2Cl2] (78) is reduced to [{Ti(Cp)2Cl}2] (92), and [TiCpCl3] (79) is reduced to [TiCpCl2(THF)] (93) (Scheme 44).[‌213‌] This preparative method has distinct advantages over the standard method which uses zinc dust as the reductant, in that it avoids the formation of the bis[chlorobis(η5-cyclopentadienyl)titanium(III)]zinc(II) chloride complex, [{Ti(Cp)2Cl}2]ZnCl2, which is often a major product. The method has advantages over the reaction between dichlorobis(η5-cyclopentadienyl)titanium(IV) (78) and [Ti(BH4)(Cp)2], since it avoids the prior preparation of the latter complex.

Meeeee 88 Meeeeeeeeee ee Meeeeeee(MMM) Meeeeeeee ee Meeeeeeee ee Meeeeeee(MM) ­Meeeeeeee ee Meeeeee Meeeeee[‌888‌]

Mee eeeeeeee ee eeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) (88) eeee eeeeeee eeeeeee ee eeeeeeeeeeeeeee ee e 8:8 eeeee eeeee ee eeeeeeeee eee eeeeeeeee ee eee-eeee eeeeeeee ee [MeMeMe8(MMM)] (88), eeee eeeee eeeeeee-eeee [(MeMeMe8)e] (88) ee eeeeeeee ee eeeeeee ee 88% eeeee. Mee eeeeeeeee ee eeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) (88) eeee eeeeeee eeeeeee ee e Me/M eeeee ee 8:8 eeeee eee eeeee, eeeeeeeeeee eeeeeee [(MeMeMe)8], eee eeeee e eeeeee eeeeeeeee eee eeee eeeeeeeee. Meee eee eeeeeeee eeeeeee eeeeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) (88) eee eeeeeee eeeeeee ee eeeeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeee, [Me(Me)8(MM)8] (888) eee ee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

Mee[eeeeeeeee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MMM)] (88):[‌888‌]

M eeeeeee ee [Me(Me)8Me8] (88; 8.8e, 8.8eeee) eee Me8M (8.8888e, 8.88eeee) (eeeee eeeee Me/M 8:8) eee eeeeee ee e Meeeeee eeee. MMM (88eM) eee eeeee eee eee eeeeeee eeeeeee eee eeeeee eeeeeee ee eeeeeeee eee eeeeeeee; eeee eeeeeeee ee eee eeeeeeeee ee e eee (eeeeeeeeee M8). Mee eeeeeee eee eeeeeeee eeeee 88eee, ee eeee ee eeeee-eeeee eeeeeeee, eeee eeeee e eeeee eeeee eee eeeeeeee eeee eee MMM eee eeeeeee eeeee eeeeeee eeeeeeee ee ee. Meeee eeeeeeee ee eeeeeee (88eM) ee eeee eeeee, eee eeeeeeee ee eee eeeeeee ee ee, e eeeeeeeeeeeeeeee eeeee eeeee eee eeeeeeee; eeeee: 8.88e (88%) (eeeeeee 88 eee eeeeeeeeee ee eeeeeeeeee eeee ee eeeeeeeee eeeeee).

Meeeeeee(η8-eeeeeeeeeeeeeeee)(eeeeeeeeeeeeeee)eeeeeeee(MMM) (88); Meeeeee Meeeeeeee:[‌888‌]

M eeeeee eeee ee [MeMeMe8] (88; 8.888e, 8.88eeee) ee MMM (88eM) eee eeeee ee e eeeeeeeeee ee Me8M (8.8888e, 8.88eeee) ee MMM (88eM) ee e Meeeeee eeee. M eeeee eeeeeeeeee eeeeeeee eeeeeeee, eeeeeeeeeee ee eee eeeeeeeee ee e eee (eeeeeeeeee M8), eee eee eeeeeee eeeeee eeeee. Meeee eee eeeeeee eee eeeeeee ee ee eee ee. 8e, eee eee Me8M eee eeeeeee, eee eee eeeeeeee eee eeeeeeeeee eeeeeeee. Meeee eee eeee eee eeeeeeee eee eee eeeeeee eee eeeeeee, e eeeee eeeee eee eeeeeeee; (eeeeeee 88 eee eeeeeeeeee ee eeeeeeeeee eeee ee eeeeeeeee eeeeee).