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Carbocations02:10

Carbocations

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Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Coordination Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Aromatic Hydrocarbon Cations: Structural Overview

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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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Conformations of Cyclohexane02:11

Conformations of Cyclohexane

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Cyclohexane does not exist in a planar form due to the high angle and torsional strain it would experience in the planar structure. Instead, it adopts non-planar chair and boat conformations.
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal...
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Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
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Metallic Solids02:37

Metallic Solids

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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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A hexanuclear gold carbonyl cluster.

Sonia Martínez-Salvador1, Larry R Falvello2, Antonio Martín1

  • 1Instituto de Síntesis Química y Catálisis Homogénea (iSQCH) , CSIC - Universidad de Zaragoza , C/Pedro Cerbuna 12 , E-50009 Zaragoza , Spain .

Chemical Science
|July 19, 2017
PubMed
Summary

Researchers synthesized a hexanuclear gold carbonyl cluster, [PPh4]2[Au6(CF3)6Br2(CO)2], through spontaneous self-assembly. This cluster features a cyclohexane-like gold(I) arrangement stabilized by strong aurophilic interactions.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Supramolecular Chemistry

Background:

  • Gold clusters are of interest due to their unique electronic and structural properties.
  • Aurophilic interactions (Au···Au) play a crucial role in the self-assembly and stability of gold complexes.
  • Understanding the factors governing the formation of multinuclear gold aggregates is essential for designing new materials.

Purpose of the Study:

  • To synthesize and characterize a novel hexanuclear gold carbonyl cluster.
  • To investigate the role of aurophilic interactions in the self-assembly process.
  • To study the structural and spectroscopic properties of the resulting gold aggregate.

Main Methods:

  • Spontaneous self-assembly of precursor gold(I) compounds.
  • Single-crystal X-ray diffraction for structural determination.
  • Infrared (IR) spectroscopy to analyze carbonyl stretching frequencies.

Main Results:

  • The hexanuclear gold cluster [PPh4]2[Au6(CF3)6Br2(CO)2] was successfully synthesized.
  • The cluster adopts a cyclohexane-like structure with a chair conformation, stabilized by strong aurophilic interactions (Au···Au ∼310 pm).
  • Significant lowering of the carbonyl stretching frequency (ν(CO)) was observed due to these interactions.

Conclusions:

  • Spontaneous self-assembly is an effective strategy for constructing complex gold clusters.
  • Aurophilic interactions are key drivers in the formation and structural organization of the hexanuclear gold aggregate.
  • The observed spectroscopic changes provide evidence for the influence of aurophilic bonding on electronic properties.