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Structural Isomerism02:34

Structural Isomerism

16.8K
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,...
16.8K
Stereoisomerism02:52

Stereoisomerism

11.0K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
11.0K
Colors and Magnetism03:02

Colors and Magnetism

12.0K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
12.0K
Valence Bond Theory02:42

Valence Bond Theory

8.8K
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...
8.8K
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

2.4K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.4K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

7.6K
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.
7.6K

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Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
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A multiply functionalized base-coordinated Ge(II) compound and its reversible dimerization to the digermene.

Anukul Jana1, Volker Huch, Henry S Rzepa

  • 1Krupp-Lehrstuhl für Allgemeine und Anorganische Chemie, Universität des Saarlandes, 66125 Saarbrücken (Germany) http://www.uni-saarland.de/fak8/scheschkewitz/index.html; New Address: Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brundavan Colony, Narsingi, Hyderabad-500075 (India).

Angewandte Chemie (International Ed. in English)
|November 4, 2014
PubMed
Summary

Researchers synthesized a novel imino-functionalized germanium(II) species using N-heterocyclic carbene (NHC) stabilization. This compound reversibly dimerizes to form a germanium-germanium bond, overcoming harsh reaction condition limitations.

Keywords:
Lewis aciddigermenegermaniuminsertionlow-valent compounds

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Area of Science:

  • Organometallic Chemistry
  • Main Group Chemistry
  • Carbene Chemistry

Background:

  • Stable germanium-germanium (Ge-Ge) bonds typically require harsh conditions incompatible with many functional groups, especially unsaturated ones.
  • Low-coordinate germanium compounds readily react with unsaturated functionalities, limiting synthetic approaches.

Purpose of the Study:

  • To develop a milder synthetic route to compounds featuring a Ge-Ge bond.
  • To synthesize and characterize novel imino-functionalized germanium(II) species.
  • To explore the reversible formation and cleavage of a Ge-Ge bond.

Main Methods:

  • Reaction of an isonitrile with an N-heterocyclic carbene (NHC)-coordinated vinylidene.
  • Stabilization of the germanium(II) species by NHC coordination.
  • Lewis acid-mediated removal of NHC to induce dimerization.
  • Reversal of dimerization via addition of NHC.

Main Results:

  • Synthesis of a novel imino-functionalized germanium(II) species stabilized by an NHC.
  • Demonstration of NHC removal leading to dimerization and formation of a Ge-Ge bond (digermene).
  • Evidence of reversible Ge-Ge bond formation and cleavage through controlled addition/removal of NHC.

Conclusions:

  • A new method for synthesizing germanium-germanium bonds under milder conditions has been established.
  • The developed NHC-stabilized germanium(II) intermediate offers a versatile platform for accessing digermenes.
  • The reversible nature of the dimerization expands the synthetic utility of these germanium compounds.