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Structural Isomerism02:34

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
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Cellular Lipid Extraction for Targeted Stable Isotope Dilution Liquid Chromatography-Mass Spectrometry Analysis
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Dodecahydroxy-closo-dodecaborate(2-).

T Peymann1, C B Knobler, S I Khan

  • 1Contribution from the Department of Chemistry and Biochemistry, University of California Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095-1569, USA.

Journal of the American Chemical Society
|July 18, 2001
PubMed
Summary
This summary is machine-generated.

The study synthesized alkali metal salts of the dodecahydroxy-closo-dodecaborate(2-) anion, finding they have surprisingly low water solubility due to cross-linking hydroxyl groups. These findings offer insights into the structural properties of boron clusters and their interactions with cations.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • The dodecahydro-closo-dodecaborate(2-) anion (closo-B(12)H(12)(2-)) is a well-studied boron cluster.
  • Functionalization of boron clusters, such as hydroxylation, can significantly alter their properties and potential applications.
  • Understanding the solubility and structural characteristics of metal salts of functionalized boron clusters is crucial for their synthesis and utilization.

Purpose of the Study:

  • To synthesize and characterize various alkali metal, ammonium, hydronium, and phosphonium salts of the dodecahydroxy-closo-dodecaborate(2-) anion.
  • To investigate the water solubility of these novel salts.
  • To elucidate the structural basis for their solubility behavior using X-ray crystallography.

Main Methods:

  • Synthesis of cesium dodecahydroxy-closo-dodecaborate(2-) (Cs(2)1) from cesium dodecahydro-closo-dodecaborate(2-) (Cs(2)2) using hydrogen peroxide.
  • Precipitation of other alkali metal (Li, Na, K, Rb), ammonium ([NH(4)](2)1), phosphonium ([PPN](2)1), and hydronium ([H(3)O](2)1) salts.
  • Determination of water solubility via Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES).
  • Solid-state characterization using single-crystal X-ray crystallography for four alkali metal salts.

Main Results:

  • Successfully synthesized Cs(2)1 and subsequently other alkali metal, ammonium, hydronium, and phosphonium salts.
  • Observed surprisingly low water solubilities for the alkali metal salts, contrary to expectations for salts derived from a dianion with hydroxyl groups.
  • Water solubility of alkali metal salts decreased with decreasing cation radius (A(+)), with a slight anomaly for lithium.
  • [H(3)O](2)1 and [NH(4)](2)1 salts represent rare examples of water-insoluble hydronium and ammonium salts.
  • X-ray crystallography revealed intricate networks where hydroxyl groups of the dianion cross-link alkali metal cations, forming aggregated salts.
  • Cation coordination numbers varied with cation radius, from ten for Cs(+) and Rb(+) to six for Na(+).
  • The core geometry of the dodecahydroxy-closo-dodecaborate(2-) anion remained consistent across different alkali metal salts.

Conclusions:

  • The pendant hydroxyl groups on the dodecahydroxy-closo-dodecaborate(2-) anion act as cross-linking ligands, leading to low water solubility of its alkali metal salts.
  • The observed low solubility is attributed to the formation of extensive hydrogen-bonded and cation-coordinated networks in the solid state.
  • The structural integrity of the boron cluster is maintained regardless of the counter-cation, highlighting the robustness of the closo-borate framework.