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Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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The ditungsten decacarbonyl dianion.

Joseph P A Ostrowski1, Benjamin E Atkinson, Laurence R Doyle

  • 1Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK. steve.liddle@manchester.ac.uk nikolas.kaltsoyannis@manchester.ac.uk.

Dalton Transactions (Cambridge, England : 2003)
|June 26, 2020
PubMed
Summary
This summary is machine-generated.

The ditungsten decarbonyl dianion was synthesized, revealing a surprising eclipsed geometry in the solid state, unlike the typical staggered form. Computational studies explain this solid-state structure arises from crystal packing effects.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Solid-State Chemistry

Background:

  • The synthesis of group 6 metal carbonyl dianions is a long-standing area of research.
  • Binary homobimetallic carbonyls typically adopt a staggered geometry.

Purpose of the Study:

  • To synthesize and structurally characterize the ditungsten decarbonyl dianion.
  • To investigate the geometric preferences of this dianion in both gas-phase and solid-state.

Main Methods:

  • Synthesis of [(OC)5W-W(CO)5][K(18-crown-6)(THF)2]2.
  • Single-crystal X-ray diffraction analysis.
  • Density Functional Theory (DFT) and Coupled Cluster (CCSD(T)) computational studies.

Main Results:

  • The ditungsten decarbonyl dianion was successfully synthesized and structurally authenticated.
  • The solid-state structure exhibits a D4h eclipsed geometry, contrasting with the gas-phase preference for the D4d staggered conformation.
  • Computational studies confirmed the D4d geometry is energetically favored in the gas phase.

Conclusions:

  • Crystal packing forces stabilize the D4h eclipsed geometry in the solid state, overriding the gas-phase energetic preference for the D4d staggered form.
  • The study completes the group 6 dianion triad, providing insights into metal-metal bonding in homobimetallic carbonyls.