2-(,-Diethylaminomethyl)-6,7-trihydroquinolinyl-8-ylideneamine-Ni() chlorides: application in ethylene dimerization and trimerization

• Published in: New journal of chemistry Vol. 44; no. 39; pp. 1747 - 1752
• Main Authors: Li, Jiaxin, Ma, Yanping, Hu, Xinquan, Flisak, Zygmunt, Tongling, Liang, Sun, Wen-Hua
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 21.10.2020
• Subjects: Aniline; Catalysts; Chemical analysis; Crystallography; Crystals; Dichlorides; Dimerization; Ethylene; Hexenes; Infrared analysis; Infrared spectroscopy; Nickel; Oligomerization; Selectivity; Single crystals; Thermal stability
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d0nj04003g

A series of Ni( ii ) complexes with the general formula [2-((NEt 2 )Me)-8-{N(Ar)}C 9 H 8 N]NiCl 2 , where Ar = 2,6-Me 2 C 6 H 3 in Ni1 , 2,6-Et 2 C 6 H 3 in Ni2 , 2,6-i-Pr 2 C 6 H 3 in Ni3 , 2,4,6-Me 3 C 6 H 2 in Ni4 , 2,6-Et 2 -4-MeC 6 H 2 in Ni5 , and 2,4,6- t -Bu 3 C 6 H 2 in Ni6 , has been prepared using a one-pot reaction of 2-( N , N -diethylaminomethyl)-6,7-dihydroquinolin-8(5 H )-one with the corresponding aniline and nickel dichloride hexahydrate. The resultant complexes were characterized using elemental analysis and FT-IR spectroscopy, while the mononuclear Ni1 and Ni3 were also the subject of single-crystal X-ray diffraction study. On activation with MMAO, the complexes Ni1-Ni6 displayed good activity in ethylene oligomerization, forming hexenes ( ca. 48% 1-hexene) as the major products and exhibiting thermal stability up to 50 °C under 10 atm C 2 H 4 . When MAO was applied as the cocatalyst, lower activity was observed, but the catalyst showed higher selectivity toward ethylene dimerization. It is also worth noticing that an induction period was observed as the Ni/MAO catalysts reached their peak activity after 30 min. The unusual influence of co-catalysts on the oligomerization of ethylene is observed with the title nickel complexes, indicating major dimerization and major trimerization with the co-catalysts MAO and MMAO, respectively.