Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system.

Chromium-based catalyst systems with polar-substituted diphosphinoamine ligands are selective for either trimerisation or tetramerisation of ethylene, depending on the position of the polar groups on the aryl rings.

In situ prepared chromium catalysts containing bulky diphosphinoamine (PNP) ligands, upon activation with MAO, are extremely efficient catalysts for the trimerisation of ethylene to 1-hexene.

Heterocyclic mono(thione), trans-bis(thione), cis-bis(thione), trans-(carbene-thione), cis-(carbene-thione), trans-(phosphine-thione) and mono(imine) complexes of rhodium(I) have been prepared and fully characterised. Chloro(eta(4)-1,5-cyclooctadiene)(L)rhodium(I)(1a, L = 1,3-diisopropyl-4,5-dimethyl-2,3-dihydro-1H-imidazol-2-thione; 1b L = 1,3,4,5-tetramethyl-2,3-dihydro-1H-imidazol-2-thione) appear as isomers at room temperature due to slow coordination exchange on the S-donor atom. In the three structures determined, the substituent on the sulfur appears syn to Cl. Hindered rotation about the Rh-carbene bond is revealed in the NMR spectra of seven new complexes with isopropyl substituents on the heterocyclic carbene ligands. The trans influence of the thione ligands is smaller than that of carbenes but larger than that shown by imines and chloride. Thione complexes are better catalyst precursors than the carbene complexes for the hydroformylation of 1-hexene under the chosen reaction conditions: 80 degrees C, 8 MPa CO-H2(1:1), 16 h, 1:1000 catalyst to 1-hexene ratio.