Solution-state and solid-state structural characterization of complexes of a new macrocyclic ligand containing the 1,5-diazacyclooctane subunit.
The synthesis and characterization of a new constrained tetraazamacrocyclic ligand, 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane (1,11-C(3)-cyclam), is reported. Because of its basicity, this ligand (pK(a) of the protonated form >13.5) requires aprotic solvents for its metalation reactions. Two complexes of this ligand, [Ni(1,11-C(3)-cyclam](OTf)(2) and [Co(1,11-C(3)-cyclam)(NCS)(2)](OTf), have been characterized by single-crystal X-ray crystallography. For the Ni(II) complex, the 1,5-diazacyclooctane (daco) subunit of the ligand is in the chair-boat conformation, whereas that same subunit in the Co(III) complex is in the chair-chair conformation. For the Ni(II) complex, C(12) and H(12a) block one of the coordination sites. The (1)H and (13)C NMR spectra of the Ni(II) complex in D(2)O have very sharp resonances, indicative of low-spin Ni(II). The resonance for H(12a) appears at 4.5 ppm, suggesting an interaction with Ni(II). In acetonitrile, the (1)H and (13)C spectra are broadened, indicative of a low-spin/high-spin equilibrium due to axial coordination by acetonitrile. C(12) experiences the greatest degree of broadening in the (13)C NMR spectrum. Variable-temperature NMR spectroscopy from -70 to +80 degrees C shows no significant change as a function of temperature. The electronic spectrum of the Ni(II) complex (lambda(max) = 449.9 nm) is consistent with steric and electronic factors for this complex.
Hu
Chuanjiang
C
Department of Chemistry, Santa Clara University, Santa Clara, California 95053, USA.
Nguyen
Thoi D
TD
Wagenknecht
Paul S
PS
Nathan
Lawrence C
LC
D000473:Alkanes / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000138:chemical synthesis; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D012997:Solvents; D013696:Temperature
C475338:1,4,8,11-tetraazabicyclo(9.3.3)heptadecane; D000473:Alkanes; D006571:Heterocyclic Compounds; D006574:Heterocyclic Compounds, 2-Ring; D008024:Ligands; D009942:Organometallic Compounds; D012997:Solvents; C024560:cyclam; D009532:Nickel