Abstract
The cyclocopolymerization of 1,6-heptadiene (HPD) with ethylene (E) by a series of half-sandwich scandium alkyl catalysts bearing various auxiliary ligands have been examined. Significant ligand influence on the copolymerization activity and selectivity was observed. In combination with one equivalent of [Ph3C][B(C6F5)4], the half-sandwich scandium dialkyl complexes bearing a Lewis base THF (1) or an NHC side arm (2) yielded the copolymer products together with cross-linked polymers in the copolymerization of HPD with ethylene. In contrast, the THF-free complexes Cp’Sc(CH2C6H4NMe2-o)2 (3: Cp’ = C5H5; 4: Cp’ = C5Me4SiMe3) and the phosphine oxide side-arm containing complex (C5Me4SiMe2CH2(O)PPh2)Sc(CH2SiMe3)2 (5) showed excellent activity and selectivity for the cyclocopolymerization reaction, without giving cross-linked products. The 1H and 13C NMR analyses revealed that the resulting copolymers consist of E-E sequences and six-membered ring methylene-1,3-cyclohexane (MCH) and five-membered ring ethylene-1,2-cyclopentane (ECP) units. The HPD content in the copolymer products could be easily controlled by changing the feeding amount of HPD under 1 atm of ethylene.
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Dedicated to Professor Qian Changtao on the occasion of his 80th birthday.
HOU ZhaoMin was born in Shandong Province, China, in 1961. He received his Ph.D. from Kyushu University in 1989 and then joined RIKEN, where he has been Chief Scientist and Director of Organometallic Chemistry Laboratory since 2002. He is now concurrently appointed to Deputy Director of RIKEN Center for Sustainable Resource Science and Guest Professor at Dalian University of Technology. His research focuses on organometallic chemistry and molecular catalysis. Recent awards include JSPS Prize (2007), the Chemical Society of Japan Award for Creative Work (2007), Mitsui Chemicals Catalysis Science Award (2007), Commendation for Science and Technology by the Minister of MEXT of Japan: the Prizes for Science and Technology (2008), the Rare Earth Society of Japan Award (2009), and the Award of the Society of Polymer Science, Japan (2012)
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Guo, F., Nishiura, M., Li, Y. et al. Cyclocopolymerization of 1,6-heptadiene with ethylene by half-sandwich scandium catalysts. Sci. China Chem. 57, 1150–1156 (2014). https://doi.org/10.1007/s11426-014-5132-9
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DOI: https://doi.org/10.1007/s11426-014-5132-9