A series of bis(peralkylindenyl)zirconocene and hafnocene complexes were synthesised and characterised by NMR spectroscopy, mass spectrometry and elemental analyses.


We report the synthesis of two zirconocenes, dimethylsilylbis(hexamethylindenyl) zirconium dichloride, rac-(SBI*)ZrCl2, and nbutyldimethylsilyl(hexamethylindenyl) zirconium trichloride, [(Ind*SiMe2nBu)Zr(μ-Cl)Cl2]2. The complexes were characterised by NMR spectroscopy and X-ray crystallography, and the bonding was evaluated using density functional theory. 



Unsymmetrical permethylindenyl bent metallocene complexes have been synthesised and reacted with inorganic solid supports to afford catalysts for the slurry phase polymerisation of ethylene. Those supported on solid polymethylaluminoxane were both highly active catalysts and afforded polymers with a desirable, low aggregation, “popcorn” morphology.


Permethylindenyl constrained geometry complexes of the type Me2SB(RN,I*)TiCl2({(η5-C9Me6)Me2Si(RN)}TiCl2; R = i-Pr, t-Bu,n-Bu, Ph, 4-t-BuPh and 4-n-BuPh). Reaction with solid polymethylaluminoxane (sMAO) yields solid catalysts active for the slurry phase polymerisation of ethylene. 


Recent publications:

Popcorn-shaped polyethylene synthesised using highly active supported permethylindenyl metallocene catalyst systems, J.-C. Buffet, Z. R. Turner and D. O’Hare, Chem. Commun. (2018), 54, 10970-10973.

Group 4 permethylindenyl constrained geometry complexes for ethylene polymerisation catalysis, T. J. Williams, J.-C. Buffet, Z. R. Turner and D. O’Hare, Catal. Sci. Technol. (2018).

Synthesis and Characterisation of Permethylindenyl zircononium Complexes and their use in ethylene polymerisation, J.-C. Buffet, T.A. Q. Arnold, P. Angpanitcharoen, Z. R. Turner, RSC Adv., (2015), 5, 87456-87464.

Synthesis, Characterisation, and Polymerisation Studies of Hexamethylindenyl Zirconocenes and Hafnocenes, T.A.Q. Arnold, J.-C. Buffet, Z.R. Turner and D. O’Hare, J. Organomet. Chem., (2015), 792, 55-56.