Synthesis, crystal structure and properties of [Co(L)2](ClO4)2 (L=1,3-bis(1H-benzimidazol-2-yl)-2-oxapropane)

Tavman, Aydın; Sayıl, Çiğdem

doi:10.2298/jsc140415081t

Cited by 2 publications

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References 27 publications

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“…Coordination of the central oxygen donor in complex [Cr(14)Cl 3 ] is unlikely, considering the very long metal oxygen distances seen in other complexes with this ligand. 37,38 A strongly coordinating central donor appears to be essential for high catalytic activity, and only sp 3 -hybridized amine donors result in an alternating olefin distribution. An sp 2 -hybridized nitrogen donor, such as pyridine in complex [Cr(17)Cl 3 ], shows a significantly lower activity and, more importantly, gives a Schulz−Flory distribution of LAOs with α = 0.87.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Alternating α-Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

et al. 2016

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The catalytic oligomerization of ethylene with chromium-based complexes containing bis(benzimidazolemethyl)amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol–1 h–1 bar–1) with N-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe3 and the N-methyl BIMA ligand 2 have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions.

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Section: ■ Results and Discussionmentioning

confidence: 99%