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Updated: May 30, 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
Synthetic and structural studies of monocyclopentadienyl cyclometalated aryl tantalum(V) compounds
Miguel Galajov1, Agustín Galindo, Carlos García
1Centro de Espectroscopia de Resonancia Magnética Nuclear, Universidad de Alcalá de Henares, Campus Universitario, E-28871, Alcalá de Henares, Spain.
Abstract:
Cyclometalated aryl tetra- or trichlorido cyclopentadienyl tantalum complexes [TaXCl(3){C(6)H(4)(2-CH(2)NMe(2))-κ(2)C,N}] (X = Cl 1, η(5)-C(5)H(5)2, η(5)-C(5)H(4)(SiMe(3)) 3, η(5)-C(5)Me(5)4) containing a five-membered TaC(3)N chelate ring were synthesized by reaction of the TaXCl(4) (X = Cl, η(5)-C(5)H(5), η(5)-C(5)H(4)(SiMe(3)), η(5)-C(5)Me(5)) with the appropriate lithium aryl reagent [Li{C(6)H(4)(2-CH(2)NMe(2))}]. The reported complexes were studied by IR and NMR spectroscopy and the X-ray molecular structures of compounds 2, 3 and 4 were determined by diffraction methods. These compounds were theoretically analyzed by the DFT method and their structures were rationalized. The preferential coordination of the 2-{(dimethylamino)methyl}phenyl ligand was justified by an analysis of the molecular orbitals of the Ta(η(5)-C(5)H(5))Cl(3) and C(6)H(4)(2-CH(2)NMe(2)) fragments. In addition, the exchange pathways that account for the NMR equivalency of the Me(2)N- methyl groups and -CH(2)- hydrogen atoms of the coordinated C(6)H(4)(2-CH(2)NMe(2))-κ(2)C,N ligand were theoretically studied.
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