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2.10.10.4.1 Variation 1: Benzynetitanium Complexes by Thermolysis of Aryl(methyl)titanium ­Complexes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 561.

An alternative and convenient method for the generation of titanium–benzyne complexes is the thermolysis of dichlorobis(η5-cyclopentadienyl)titanium(IV) (‌78‌) with aryl Grignard reagents. Buchwald has isolated trimethylphosphine-stabilized benzynetitanium complex ‌259‌ (‌Scheme 126‌), formed by thermolysis of aryltitanium complex ‌258‌ in the presence of trimethylphosphine. Further treatment of benzynetitanium ‌259‌ with methyllithium in the presence of alkenes gives benzotitanacyclopentanes.[‌373‌,‌374‌] Trimeth­ylphosphine-free benzynetitanium complex ‌260‌ reacts with various unsaturated compounds (e.g., EtC≡CEt, p-BrC6H4CN, AcCH=CH2, H2C=CH2) to give five-membered metallacycles.

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M eeee ee [MeMe(Me)8(8-MeMM8M8)] (‌888‌; 8.8 e, 88 eeee) eee Me8M (8 eM, ee. 88 eeee) ee eeeeeee (88 eM) (MMMMMMM: eeeeeee ee eeeeeeeeeeee!) eee eeeeee ee 88°M eee 88 e, eeeeee eeeee eeee eee eeeee ee eee eeeeeee eeeeeee ee eeeeee-eeeee. Meeee eee eeeeeee eee eeee eeeeee eee eee eeeeeeeee eee eeee eeeeeee eeeee eeeeee, eee eeeeeee eee eeeeeeeee eeee eeeeeee (88 eM) eee eee eeeeeee eee eeeeeeee eee eeeeee ee −88°M eee 88 e. Mee eeeeee eeeeee eee eeeeeeeee eeee eee eeeeeeee, eeeee eeee eeeeee eeee eeeeeee (8 × 88 eM) eeeee eee eeeee eeeee eeeeeeeeeee, eeeeeee e eeeeee eeeee (8.8 e). Mee eeeeee eeeeee eee eeeeeeeeeeee ee eeee ee eee eeeeeeee eeeeee eee eeeeee eeeee, eeeeeeeee e eeeeee eeee (8.88 e), eeeee eee eeeeee ee eee eeee eee. Meeeeee ‌888‌ eee eeeeeeee ee e eeeeeee ee eeee-‌888‌/eee-‌888‌ (8:8 ee 8M MMM); eeeee: 8.88 e (88%); MM (Meeee) νeee: 8888.8 (e, eeeeeeee M=M) 888.8 (e, M—M) ee−8; 8M MMM (eeeeeee-e8, −88°M, δ): eeee-‌888‌: 8.88 (ee, M = 8.8, 8.8 Me, 8M, MM eeee), 8.88 (e, M = 8.8 Me, 8M, MM eeee), 8.88 (e, M = 8.8 Me, 8M, MM eeee), 8.88 (e, 88M, Me), 8.88 (e, 8M, MMM8), 8.88 [e, 8M, MMM = 8.8 Me, M(MM8)8]; eee-‌888‌: 8.88 (ee, M = 8.8 Me, 8M, MM eeee), 8.88 (e, M = 8.8 Me, 8M, MM eeee), 8.88 (e, M = 8.8 Me, 8M, MM eeee), 8.88 (e, 88M, Me), 8.88 (e, 8M, MMM8), 8.88 [e, 8M, MMM = 8.8 Me, M(MM8)8].

References

[373] Máeeeee, M.; Meeeeeee, M. M., Meeeeeeeeeeeeee, (8888), 88, 8888.
[374] Meee, M.; Meee, M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888.

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

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