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Updated: Feb 25, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Formation of Binuclear Zigzag Hexapentaene Titanium Complexes via a Titanacumulene [Ti=C=C=CH2 ] Intermediate
Tim Oswald1, Tina Gelert1, Christian Lasar1
1Institut für Chemie, Fakultät für Mathematik und Naturwissenschaften, Carl von Ossietzky-Universität Oldenburg, Postfach 2503, 26111, Oldenburg, Germany.
Abstract:
The reaction of bis(η5 :η1 -pentafulvene)titanium complexes with an allylidenephosphorylide Ph3 P=C(H)- C(H)=CH2 leads to binuclear zigzag hexapentaene titanium complexes (Ti2a, Ti2b). The formation of the central C6 H4 unit can be described as a spontaneous double C-H bond activation process, leading to an R3 P=C=C=CH2 intermediate, as a synthon for a titanabutatriene fragment [(CpR )2 Ti=C=C=CH2 ] (R: 2-adamantyl, CH(p-tol)2 ). In a subsequent dimerization Ti2a and Ti2b are formed, proofed by single-crystal X-ray diffraction and NMR measurements. The reaction sequence is confirmed by DFT calculations.
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