Аннотация:We elaborated a synthetic approach to a new family of PNP ligands that involves assembling sequential molecules based on the rigid 5,6-dihydrodibenzo[c,e][1,2]-azaphosphinine backbone (−Z−). This approach allowed us to obtain PNP-type ligands of the general formula Ar2P−Z−Ar′(Ar, Ar′ = Ph, o-MeOC6H4) with high yields and without the formation of PPN byproducts. Ar2P−Z−Ar′/Cr(acac)3 (acac = acetylacetonate) adducts activated by modified methylalumoxane(MMAO-12) effectively catalyzed ethylene oligomerization; the number of ortho-methoxyphenyl fragments n controls the direction of the process, from slow polymerization (n = 0)to rapid oligomerization (n = 3), thereby producing a mixture of 1-hexene and 1-octene in ∼2:1 ratio with very low formation of polyethylene (∼0.6%).