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Title: Electronic Influence of the Thienyl Sulfur Atom on the Oligomerization of Ethylene by Cobalt(II) 6-(Thienyl)-2-(imino)pyridine Catalysis
Authors: Claudio, Bianchini
Dante, Gatteschi
Giuliano, Giambastiani
Itzel Guerrero, Rios
Andrea, Ienco
Laschi, Franco 
Carlo, Mealli
Andrea, Meli
Lorenzo, Sorace
Alessandro, Toti
Francesco, Vizza
Issue Date: 2007
Project: None 
The position of the sulfur atom in the thienyl group of 6-(thienyl)-2-(imino)pyridine ligands stronglyaffects the catalytic activity of the corresponding tetrahedral high-spin dihalide CoII complexes in theoligomerization of ethylene to R-olefins upon activation with methylaluminoxane (MAO). Complexeswith the sulfur atom in the 3-position of the thienyl ring catalyze the selective conversion of ethylene to1-butene, while catalysts containing thien-2-yl groups give C4-C14 R-olefins. In situ EPR experimentsshowed the occurrence of a spin state changeover with the formation of low-spin CoII species uponactivation of the catalyst precursors by MAO. DFT calculations suggest that only thien-2-yl rings allowfor the coordination of the sulfur atom to the cobalt center in the MAO-activated systems.
ISSN: 0276-7333
DOI: 10.1021/om0609665
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