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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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...
Aromatic Hydrocarbon Cations: Structural Overview01:18

Aromatic Hydrocarbon Cations: Structural Overview

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.
Removing one hydrogen from the intervening CH2 group with both...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Carbocations02:10

Carbocations

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...
Aromatic Hydrocarbon Anions: Structural Overview01:18

Aromatic Hydrocarbon Anions: Structural Overview

Neutral hydrocarbons like cyclopentadiene with an odd number of carbon atoms and one intervening CH2 group in the ring are not aromatic. Cyclopentadiene with 4 π electrons does not satisfy the 4n + 2 π electron rule. Additionally, the intervening CH2 group is sp3 hybridized and lacks a vacant p orbital, thereby interrupting the overlap of p orbitals in a continuous manner and preventing the delocalization of π electrons throughout the ring.
Due to the absence of continuous overlap of p...

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Related Experiment Video

Updated: Jun 13, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
10:44

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Published on: April 19, 2019

Supraicosahedral indenyl cobaltacarboranes.

Greig Scott1, Amelia McAnaw, David McKay

  • 1Department of Chemistry, Heriot-Watt University, Edinburgh, UK EH14 4AS.

Dalton Transactions (Cambridge, England : 2003)
|May 5, 2010
PubMed
Summary

New indenyl cobaltacarboranes were synthesized and characterized, revealing insights into their structures and electronic properties. These compounds exhibit unique ligand orientations and metal-based reductions, advancing the understanding of metallacarborane chemistry.

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Area of Science:

  • Organometallic Chemistry
  • Carborane Chemistry
  • Coordination Chemistry

Background:

  • Carboranes are versatile cage compounds with diverse applications.
  • Indenyl ligands offer unique electronic and steric properties in organometallic complexes.
  • Cobaltacarboranes represent an important class of metallacarboranes with potential catalytic activity.

Purpose of the Study:

  • To synthesize and characterize novel 13-vertex indenyl cobaltacarboranes with different architectures.
  • To investigate the structural and electronic properties of these new compounds.
  • To explore the influence of ligand orientation and substituents on the reactivity and reduction potentials.

Main Methods:

  • Synthesis via reduction of closo carboranes and metallation with an indenyl cobalt fragment.
  • Characterization using mass spectrometry, NMR spectroscopy ((1)H and (11)B), and elemental analysis.
  • Structural determination through X-ray crystallography for nine compounds.
  • Electrochemical studies including spectroelectrochemistry and EPR measurements.

Main Results:

  • Successful synthesis of indenyl cobaltacarboranes with 4,1,6-, 4,1,10-, and 4,1,2-CoC(2)B(10) architectures, including methylated and tethered variants.
  • Structural analysis revealed docosahedral cages for most isomers, with a tendency for indenyl ligand orientation to be trans to cage boron atoms, influenced by substituents.
  • Electrochemical studies showed two stepwise, 1-electron reductions assigned to metal-based Co(III)/Co(II)/Co(I) couples, which are isomer-dependent.

Conclusions:

  • The synthesized indenyl cobaltacarboranes display distinct structural features and electronic properties.
  • The orientation of the indenyl ligand is influenced by steric factors and computational predictions.
  • The reduction processes are primarily metal-centered and sensitive to the carborane cage structure and isomerism.