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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
Abstract
N,N'-Di-tert-butyl-carbodi-imide, Me3CN=C=NCMe3, undergoes reductive cleavage in the presence of the GdII complex, [K(18-crown-6)2][GdII(NR 2)3] (R = SiMe3), to form a new type of ligand, the tert-butyl-cyanamide 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-butyl-cyanamide anions, (Me3CNCN)-. The crystal contains [K(18-crown-6)(H2O)][NCNCMe3-kN], in which one ( t BuNCN)- 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-butyl-cyanamidato)(1,4,7,10,13,16-hexa-oxa-cyclo-octa-deca-ne)potas-sium(I)-(tert-butyl-cyanamidato)(1,4,7,10,13,16-hexa-oxa-cyclo-octa-deca-ne)potas-sium(I)-N,N'-di-tert-butyl-carbodi-imide (1/1/1) [K(C5H9N2)(C12H24O6)]·[K(C5H9N2)(C12H24O6)(H2O)]·C9H20N2.
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