The Redox Chemistry of [Co6C(CO)15]2鈥?/sup>: A Synthetic Route to New Co-Carbide Carbonyl Clusters
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- 作者：Iacopo Ciabatti ; Cristina Femoni ; Mohammad Hayatifar ; Maria Carmela Iapalucci ; Giuliano Longoni ; Calogero Pinzino ; Matilde Valeria Solmi ; Stefano Zacchini
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：April 7, 2014
- 年：2014
- 卷：53
- 期：7
- 页码：3818-3831
- 全文大小：554K
- 年卷期：v.53,no.7(April 7, 2014)
- ISSN：1520-510X
文摘
The oxidation and reduction reactions of [Co6C(CO)15]2鈥?/sup> have been studied in detail, leading to the isolation of several new Co-carbide carbonyl clusters. Thus, [Co6C(CO)15]2鈥?/sup> reacts in tetrahydrofuran (THF) with oxidants such as HBF4路Et2O and [Cp2Fe][PF6], resulting first in the formation of the previously reported [Co6C(CO)14]鈭?/sup>; then, in CH2Cl2, the new dicarbide [Co11C2(CO)23]2鈥?/sup> is formed. The latter may be further oxidized, yielding the isostructural monoanion [Co11C2(CO)23]鈭?/sup>, whereas its reduction with (cyclopentadienyl)2Co affords the unstable trianion [Co11C2(CO)23]3鈥?/sup>, which decomposes during workup. Oxidation of [Co6C(CO)15]2鈥?/sup> in CH3CN with [C7H7][BF4] affords the same major products, and besides, the new monoacetylide [Co10(C2)(CO)21]2鈥?/sup> was obtained as side-product. Conversely, the reduction of [Co6C(CO)15]2鈥?/sup> in THF with increasing amounts of Na/naphthalene results in the following species: [Co6C(CO)13]2鈥?/sup>, [Co11(C2)(CO)22]3鈥?/sup>, [Co7C(CO)15]3鈥?/sup>, [Co8C(CO)17]4鈥?/sup>, [Co6C(CO)12]3鈥?/sup>, and [Co(CO)4]鈭?/sup>. The new [Co11C2(CO)23]鈭?/sup>, [Co11C2(CO)23]2鈥?/sup>, [Co10(C2)(CO)21]2鈥?/sup>, [Co8C(CO)17]4鈥?/sup>, [Co6C(CO)12]3鈥?/sup>, and [Co7C(CO)15]3鈥?/sup> clusters were structurally characterized. Moreover, the paramagnetic species [Co11C2(CO)23]2鈥?/sup> and [Co6C(CO)12]3鈥?/sup> were investigated by means of electron paramagnetic resonance spectroscopy. Finally, electrochemical studies were performed on [Co11C2(CO)23]n鈭?/sup> (n = 1鈥?).