Reactivity of Hydride Bridges in High-Spin [3M鈥?(渭-H)] Clusters (M = FeII, CoII)
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- 作者：Yousoon Lee ; Kevin J. Anderton ; Forrest T. Sloane ; David M. Ermert ; Khalil A. Abboud ; Ricardo Garc铆a-Serres ; Leslie J. Murray
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：August 26, 2015
- 年：2015
- 卷：137
- 期：33
- 页码：10610-10617
- 全文大小：480K
- ISSN：1520-5126
文摘
The designed [3M鈥?(渭-H)] clusters (M = FeII, CoII) Fe3H3L (1-H) and Co3H3L (2-H) [where L3鈥?/sup> is a tris(尾-diketiminate) cyclophane] were synthesized by treating the corresponding M3Br3L complexes with KBEt3H. From single-crystal X-ray analysis, the hydride ligands are sterically protected by the cyclophane ligand, and these complexes selectively react with CO2 over other unsaturated substrates (e.g., CS2, Me3SiCCH, C2H2, and CH3CN). The reaction of 1-H or 2-H with CO2 at room temperature yielded Fe3(OCHO)(H)2L (1-CO2) or Co3(OCHO)(H)2L (2-CO2), respectively, which evidence the differential reactivity of the hydride ligands within these complexes. The analogous reactions at elevated temperatures revealed a distinct difference in the reactivity pattern for 2-H as compared to 1-H; Fe3(OCHO)3L (1-3CO2) was generated from 1-H, while 2-H afforded only 2-CO2.