Single-site chromium catalysts for olefin polymerization with donor functionalized cyclopentadienyl (Cp) ligands have been modified in order to improve their incorporation ability for the comonomer 1-hexene into the polymer chain under maintenance of their very high catalytic activities. A trimethylsilyl substituent in combination with a fused thiophene ring at the Cp ligand has been identified as the best ligand so far, leading to a doubling in 1-hexene incorporation and polyethylene (PE) with up to 27% 1-hexene content (by weight) has been obtained. The complexes lead to PE with molecular weight in the range of 50 000 to 800 000 g mol(-1) when used in homogeneous solution, however after supporting the complex on silica ultrahigh molecular weight polyethylene (UHMW-PE) is formed with 9.9% of 1-hexene incorporated into the chain. Although other known catalysts incorporate even more 1-hexene, the presented system is different as it combines considerable a-olefin incorporation with very high polymer molecular weights and very high catalytic activity. These improved single-site chromium catalysts maintain their advantageous properties on silica as solid support which makes them good candidates for their application in industrial processes for the synthesis of polyethylene materials with advanced properties.