Cofacial dicobalt complex of a binucleating hexacarboxamide cryptand ligand. 2010

Glen E Alliger, and Peter Müller, and Christopher C Cummins, and Daniel G Nocera
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.

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.

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