CC BY-NC-ND 4.0 UnportedRosenthal, Uwe2021-09-062021-09-062019https://oa.tib.eu/renate/handle/123456789/6707https://doi.org/10.34657/5754Many examples exist for the chromium catalyzed selective ethylene oligomerization in which the influence of ligands is essential for the formation of products. Regarding the tri- and tetramerization to 1-hexene or 1-octene mostly PNP ligands are responsible for the tetra- and some of such modified ligands for the trimerization. A very special case in these reactions are PNPN−H ligands, showing in most cases highly selective trimerization of ethylene to 1-hexene. In this review all existing published information about these PNPN−H ligands is accumulated and compared to some other related PNP, PNPN and NPNPN ligands in the chromium catalyzed selective ethylene oligomerization with respect to the switch from tetra- to trimerization and back by different substituent pattern of PNP ligand. Mechanistic information and arguments are collected to explain the switch from tetra- to trimerization and back by substitution of functional groups in classical PNP to PNPN−H ligands as a result of mono- and dinuclear catalytic species. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.enghttps://creativecommons.org/licenses/by-nc-nd/4.0/540homogeneous catalysismechanismorganometallic chemistryphosphorus ligandsselective oligomerizationArticle