Rational design of ansa-heterocenes with a long SiOSi bridge as a catalysts for selective dimerization of oct-1-eneстатья
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Дата последнего поиска статьи во внешних источниках: 8 мая 2024 г.
Аннотация:Being activated by methylalumoxane ([Al]/[Zr] =10), (η5-C5H5)2ZrCl2 (Zr1) and [(η5-C5H4SiMe2)2O]ZrCl2 (Zr2) catalyze selective dimerization of α-olefins with low productivity (turnover number TON ~2000). Our previous research of heterocycle-fused ansa-zirconocenes revealed that SiMe2-bridged complexes catalyze polymerization of α-olefins, whereas CH2CH2-bridged complexes are high-performance oligomerization catalysts (TON ~ 4•105). We proposed that further elongation of the bridge will allow obtaining dimerization catalysts. New –SiMe2OSiMe2– bridged ansa-zirconocenes Zr3–Zr11 were synthesized and studied in oct-1-ene dimerization at 100 ◦C and [oct-1-ene]/[Zr] ratio of 3•104. In the absence of H2 bis(5,6-dihydroindeno[2,1-b]indole) derivatives Zr8 and Zr9 demonstrated high activity and dimerization selectivity up to 94%. In the presence of H2 symmetrical indenoindole complexes Zr5–Zr9 appeared to be even more active, but up to 24% of hydrogenated oct-1-ene dimer HC16 was formed. Mixed-ligand complexes Zr10 and Zr11 catalyzed oct-1-ene dimerization with up to 99% selectivity without the formation of HC16 even in trace amounts.