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Synthesis and Reactivity of Titanocene Methylene Complexes and Bis(η⁵-Cyclopentadienyl) Titanacyclobutenes


Meinhart, James Douglas (1987) Synthesis and Reactivity of Titanocene Methylene Complexes and Bis(η⁵-Cyclopentadienyl) Titanacyclobutenes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/16dt-2465.


Syntheses of several bis(η5-cyclopentadienyl) titanium methylene phosphine complexes are reported. The titanium methylene phosphine complexes are generated from themolysis of titanacyclobutanes in the presence of excess phosphine. Spectral data and reactivity are consistent with a methylene phosphine complex rather than an ylide complex.

Bis(η5-cyclopentadienyl) titanacyclobutenes are readily synthesized by treatment of sources of "Cp2TiCH2" with disubstituted alkynes. A variety of stable titanacyclobutenes were synthesized containing aryl, alkyl, and etherial substituents. Titanacyclobutenes, unlike the related titanacyclobutanes, do not reform "Cp2TiCH2" thermally.

Titanacyclobutenes insert carbon monoxide, forming an acyl intermediate which rearranges to a titanocene vinyl ketene complex. A trimethylphosphine adduct of one of the ketene complexes was characterized by x-ray diffraction techniques. The carbonylation mechanism involves insertion of carbon monoxide into the more accessible titanium-carbon bond, followed by intra-molecular attack of the vinyl group to the acyl. Insertion of t-butyl isocyanide into a titanacyclobutene yields a cyclic imino-acyl complex, which was also characterized by x-ray diffraction. The vinyl ketene complexes react with many unsaturated substrates (alkynes, ethylene, and aldehydes) to form new organotitanium species.

Titanacyclobutenes react with ketones and aldehydes via 1,2-addition to yield titanium oxacyclohexenes. Aldehydes form both titanium-oxygen and titanium-carbon regioisomers. The organic ligand may be removed from the titanium to give homo-allylic alcohols in good yield. Nitriles also insert into titancyclobutenes to roduce titanium imidocyclohexenes.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Grubbs, Robert H.
Thesis Committee:
  • Dervan, Peter B. (chair)
  • Grubbs, Robert H.
  • Goddard, William A., III
  • Bercaw, John E.
Defense Date:26 November 1986
Additional Information:Thesis title listed in 1987 commencement program varies from actual thesis: Synthesis and Reactivity of Titanocene Methylene Complexes and Bis(Cyclopentadienyl) Titanacyclobutenes.
Funding AgencyGrant Number
Earl C. Anthony FellowshipUNSPECIFIED
Record Number:CaltechTHESIS:10212019-165401033
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11837
Deposited By: Mel Ray
Deposited On:22 Oct 2019 00:10
Last Modified:16 Apr 2021 22:12

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