Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
Inorg Chem. 2010 Apr 19;49(8):3697-9. doi: 10.1021/ic100395a.
A hexacarboxamide cryptand featuring appended polyether moieties is used as a binucleating ligand for two Co(II) centers, marking the first time cryptands have been used as hexaanionic N donors for metal coordination. A synthesis for the hexacarboxamide cryptand, culminating in a 23% yield high-dilution step and proceeding in 8% overall yield, is reported. The ligand is metalated using cobalt(II) acetate, and a solid-state structure is presented, revealing an intermetallic void over 6.4 A in length. The reactivity of this new type of cryptate is also probed; treatment of the dicobalt cryptate with potassium cyanide at elevated temperature results in a bridging cyanide complex.
一种带有附加聚醚部分的六羧酸酰胺cryptand 被用作两个 Co(II) 中心的双核配体，这标志着 cryptand 首次被用作金属配位的六阴离子 N 供体。报道了一种六羧酸酰胺 cryptand 的合成方法，最终采用 23%的产率进行高稀释步骤，总产率为 8%。该配体用乙酸钴进行金属化，并呈现出一个固态结构，揭示了一个超过 6.4Å 的金属间空隙。还研究了这种新型 cryptate 的反应性；将二钴 cryptate 与氰化钾在高温下处理会导致桥接氰化物配合物。
