Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
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Authors: | Uwe Bayer Adrian Jenner Jonas Riedmaier Ccilia Maichle-Mssmer Reiner Anwander |
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Institution: | Institute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany; (U.B.); (A.J.); (J.R.); (C.M.-M.) |
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Abstract: | Homoleptic ceric pyrazolates (pz) Ce(RR’pz)4 (R = R’ = tBu; R = R’ = Ph; R = tBu, R’ = Me) were synthesized by the protonolysis reaction of CeN(SiHMe2)2]4 with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO2, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO2 insertion was found to increase in the order of tBu2pz < Ph2pz < tBuMepz < Me2pz. For comparison, the pyrrole-based ate complexes Ce2(pyr)6(µ-pyr)2(thf)2]Li(thf)4]2 (pyr = pyrrolato) and Ce(cbz)4(thf)2]Li(thf)4] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex CeN(SiHMe2)2]4Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO2 seemed promising, but any reversibility could not be observed. |
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Keywords: | cerium pyrazoles pyrroles carbazoles carbon dioxide |
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