Reductive cleavage of N,N′-di-tert-butylcarbodiimide generates tert-butylcyanamide ligands, (Me3CNCN)−, that bind potassium both end-on and side-on in the same single crystal

• Main Authors: Amanda B. Chung, Joseph W. Ziller, William J. Evans
• Format: Article
• Language: English
• Published: International Union of Crystallography 2020-07-01
• Series: Acta Crystallographica Section E: Crystallographic Communications
• Subjects: carbodiimide; cyanamide; urea; 18-crown-6; potassium; crystal structure
• Online Access: http://scripts.iucr.org/cgi-bin/paper?S205698902000732X

N,N′-Di-tert-butylcarbodiimide, Me3CN=C=NCMe3, undergoes reductive cleavage in the presence of the GdII complex, [K(18-crown-6)2][GdII(NR2)3] (R = SiMe3), to form a new type of ligand, the tert-butylcyanamide anion, (Me3CNCN)−. This new ligand can bind metals with one or two donor atoms as demonstrated by the isolation of a single crystal containing potassium salts of both end-on and side-on bound tert-butylcyanamide anions, (Me3CNCN)−. The crystal contains [K(18-crown-6)(H2O)][NCNCMe3-kN], in which one (tBuNCN)− anion is coordinated end-on to potassium ligated by 18-crown-6 and water, as well as [K(18-crown-6)][η2-NCNCMe3], in which an 18-crown-6 potassium is coordinated side-on to the terminal N—C linkage. This single crystal also contains one equivalent of 1,3-di-tert-butyl urea, (C9H20N2O), which is involved in hydrogen bonding that may stabilize the whole assembly, namely, aqua(tert-butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–(tert-butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–N,N′-di-tert-butylcarbodiimide (1/1/1) [K(C5H9N2)(C12H24O6)]·[K(C5H9N2)(C12H24O6)(H2O)]·C9H20N2.