Research Article

Synthesis of Biomimetic Zinc Complexes for CO2 Activation and the Influence of Steric Changes in the Ttz Ligands [Ttz = Tris(triazolyl)borate]

Published: 2016-6

Journal: European Journal of Inorganic Chemistry

DOI: 10.1002/ejic.201500819

Abstract

Carbon dioxide fixation with zinc complexes of the anionic tris(triazolyl)borate (Ttz) ligand offers biomimetic structures in a hydrophilic environment. However, the synthetic result depends greatly on the steric bulk of the Ttz ligand. Synthetic routes adapted from the synthesis of (Tp)ZnOH have been applied to bulky Ttz ligands, but side products often result because Ttz frequently forms complexes with +1 metals or cations used in the synthesis. Nonetheless, (TtztBu,Me)ZnOH (1) has been successfully synthesized and crystallographically characterized, but only via the hydrolysis of the zinc (hexamethylsilyl)azide complex (6). With less bulky ligands, namely TtzPh,Me, routes expected to form LZnOH lead instead to bis(ligand) products, namely [(TtzPh,Me)2Zn] (12). The use of ligands of intermediate steric bulk has led to the isolation of (TtziPr2)ZnOH (2a) which fixes atmospheric CO2to produce [(TtziPr2)Zn]2(μ‐η1‐η2‐CO3) (2b). This activation of CO2from air is irreversible. We report the crystal structures of2band related molecules used for synthesis and structural comparison: (TtziPr2)ZnCl (7), [(TtziPr2)Cu(μ‐OH)]2(9), and [(TtziPr2)Cu(μ‐Cl)]2(10).

Faculty Members

  • Mukesh Kumar - Department of Chemistry Drexel University 3141 Chestnut St. 19104 Philadelphia PA USA
  • Brittany W. Rowe - Department of Chemistry Salisbury University 1101 Camden Ave. 21801 Salisbury MD USA
  • Matthias Zeller - Department of Chemistry Youngstown State University One University Plaza 44555 Youngstown OH USA
  • Kirsten R. Wells - Department of Chemistry Salisbury University 1101 Camden Ave. 21801 Salisbury MD USA
  • Jodi S. Kraus - Department of Chemistry Drexel University 3141 Chestnut St. 19104 Philadelphia PA USA
  • Sopheavy Siek - Department of Chemistry The University of Alabama Box 870336 35487‐0336 Tuscaloosa Alabama USA
  • Steven P. Kelley - Department of Chemistry The University of Alabama Box 870336 35487‐0336 Tuscaloosa Alabama USA
  • Natalie A. Dixon - Department of Chemistry Drexel University 3141 Chestnut St. 19104 Philadelphia PA USA
  • Elizabeth T. Papish - Department of Chemistry The University of Alabama Box 870336 35487‐0336 Tuscaloosa Alabama USA
  • Glenn P. A. Yap - Department of Chemistry and Biochemistry University of Delaware 102 Brown Laboratory 19716 Newark DE USA

Themes

  • Carbon dioxide fixation
  • Crystallographic characterization
  • Biomimetic structures
  • Zinc complexes
  • Steric effects in ligand synthesis

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