Adsorption of Metallocenes on Silica Academic Article uri icon


  • The adsorption of the metallocenes ferrocene, doubly deuterated ferrocene, cymantrene and nickelocene, as well as molybdenum hexacarbonyl, proceeds in the absence of a solvent. Large single pieces of silica gel were placed in contact with the solid metallocenes and the adsorption process was visualized on a macroscopic scale and the maximal loadings were determined. 1 H, 2 H, and 13 C solid-state NMR studies confirmed fast isotropic reorientation of the surface-adsorbed metallocene molecules within the pores of the silica. All prevalent anisotropic solid-state interactions were averaged out. The solid diamagnetic and paramagnetic materials were amenable to measurements with a standard solution NMR instrument. All metallocenes adsorbed in a monolayer. In the case of ferrocene and cymantrene, different 13 C MAS signals were obtained for the cyclopentadienyl ring carbon nuclei and assigned to one ring interacting with the surface and one ring pointing away from it. The relative adsorption strengths of ferrocene on different silica supports, nanotubes, and activated carbon were determined by a novel straightforward method recording the desorption temperature. The reversibility of adsorption has been demonstrated by competition experiments using ferrocene, doubly deuterated ferrocene, and cymantrene. Adsorbed nickelocene could be reduced to small Ni0 aggregates on the surface and the catalytic activity of the resulting material for the cyclotrimerization of phenylacetylene was proven.

altmetric score

  • 0.75

author list (cited authors)

  • Cluff, K. J., & Bl├╝mel, J.

citation count

  • 7

publication date

  • November 2016