SCG-OXFORD CENTRE OF EXCELLENCE

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:

 

Group 4 permethylindenyl complexes for the polymerisation of L‑ and rac‑lactide monomers, J.V. Lamb, J.E. Matley, C.M.R. Wright, Z.R. Turner, J.‑C. Buffet and D. O'Hare, Dalton Trans., (2019), 48, 2510-2520. 

Group 4 permethylindenyl complexes for slurry-phase polymerisation of ethyleneJ.V. Lamb, J.-C. Buffet, Z.R. Turner and D. O'Hare, Polym. Chem., 2019, 10, 1386-1398.

Synthesis, characterisation and slurry phase ethylene polymerisation of rac-(PhBBI*)ZrClimmobilised on modified layered double hydroxides, G.E. Hickman, C.M.R. Wright, A. F.R. Kilpatrick, Z.R. Turner, J.-C. Buffet, D. O’Hare, Mol. Catal., (2019), 468, 139-147. 

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.