Chromium-Based Complexes Bearing N-Substituted Diphosphinoamine Ligands for Ethylene Oligomerization

A range of novel N-substituted diphosphinoamine (PNP) ligands Ph₂PN(R)PPh₂ [R = F₂CHCH₂ (1); R = Me₂CHCH₂ (2); R = Me₂CHCH₂CH₂ (3)] have been synthesized via one-step salt elimination reaction. The ligand-coordinated chromium carbonyls [Ph₂PN(R)PPh₂]Cr(CO)₄ (4-6) were further synthesized, and X-ray crystallography analysis of complex 6 revealed the κ²-P,P bidentate binding mode of Cr center and the molecular structure of PNP ligand 3. Then the catalytic ethylene oligomerization behaviors of PNP ligands 1-3 bridging chromium chloride complexes {[Ph₂PN(R)PPh₂]CrCl₂(μ-Cl)}₂ (7-9) were further discussed in depth. Experimental results showed that complex 7 with the strong electron-withdrawing F₂CHCH₂ group can promote the nonselective ethylene oligomerization, while both complex 8 and complex 9 with the electron-donating Me₂CHCH₂ and Me₂CHCH₂CH₂ groups can significantly enhance the selective ethylene tri/tetramerization. The good catalytic activity of 198.3 kg/(g Cr·h), the selectivity toward 1-hexene and 1-octene of 76.4%, and the low PE content of 0.2% were simultaneously achieved with the Al/Cr molar ratio of 600 using the complex 8/MMAO system at 45 °C and 45 bar. These excellent results were mainly attributed to the fact that the β-branching of bridging ligand 2 increased the steric bulk of the N-moiety for complex 8.