Hexadentate ligand

A hexadentate ligand (or sexidentate ligand) is a ligand that combines with a central metal atom with six bonds. Such ligands are desirable because they have high affinities for metal ions as expressed in their formation constants.

Examples

  • Aminopolycarboxylates comprise a major class of hexadentate ligands. A commercially important member is EDTA, a tetraanion.
  • Siderophores are naturally occurring ligands secreted by organisms to bind iron, required by the organism's metabolism. Those of the catecholate and hydroxamate types are often hexadentate.[2]
  • Crown ethers are often hexadentate, presenting six ether donors. For example 18-crown-6 tightly binds K+ and NH4+ ions. Related thiacrowns and aza-crown ethers are also known. Several antibiotics are hexadentate ligands with comparable polyether bonding motifs.[3] Several polyether antibiotics function as hexadentate ligands.[4]

Nomenclature

In coordination chemistry, the denticity of hexadentate ligands is often denoted with the prefix κ6.

Topology

The arrangement of the donor atoms in hexadentate ligands, its topology, strongly affects the stability of its complexes. Some topologies are simple, such as the linear or ring shapes. The ligand can also be branched, either at a donor atom, or at a non-donor atom. Example shapes are the tripod, and amplector, with a bifurcation at each end. Rigid molecules can be used to force unusual coordination such as trigonal prism.[5] F. Lions identified 36 different hexadentate topologies.[6]

References

  1. ^ Hamilton, J. A.; Sabesan, M. N.; Steinrauf, L. K. (1981). "Crystal structure of valinomycin potassium picrate: Anion effects on valinomycin cation complexes". Journal of the American Chemical Society. 103 (19): 5880–5885. doi:10.1021/ja00409a043.
  2. ^ Cornelis P, Andrews SC, eds. (2010). Iron Uptake and Homeostasis in Microorganisms. Caister Academic Press. ISBN 978-1-904455-65-3.
  3. ^ George W Gokel, J Fraser Stoddart, ed. (2006). Crown Ethers and Cryptands. doi:10.1039/9781788010917. ISBN 978-0-85186-996-4.
  4. ^ Rutkowski, Jacek; Brzezinski, Bogumil (2013). "Structures and Properties of Naturally Occurring Polyether Antibiotics". BioMed Research International: 1–31. doi:10.1155/2013/162513. PMC 3613094. PMID 23586016.
  5. ^ Sharrad, Clint A.; Lüthi, Stefan R.; Gahan, Lawrence R. (2003). "Embracing ligands. A synthetic strategy towards new nitrogen–thioether multidentate ligands and characterization of the cobalt(III) complexes" (PDF). Dalton Trans. (19): 3693–3703. doi:10.1039/b304914k.
  6. ^ Lions, F. (1961). "The design of multidentate chelating agents". Record of Chemical Progress. 22: 69–78. ISSN 0034-1584. PMID 13762531.


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