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Alkali Metals03:06

Alkali Metals

24.6K
Group 1 elements are soft and shiny metallic solids. They are malleable, ductile, and good conductors of heat and electricity. The melting points of the alkali metals are unusually low for metals and decrease going down the group, while the density increases going down the group with the exception of potassium (Table 1).
Table 1: Properties of the alkali metals
24.6K
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

848
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
848
Preparation of Amides01:29

Preparation of Amides

4.0K
Amides are synthesized by treating carboxylic acids with amines in the presence of dehydrating agents like dicyclohexylcarbodiimide (DCC).
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
4.0K
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

24.3K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
24.3K
Bonding in Metals02:32

Bonding in Metals

52.4K
Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”. 
52.4K
Metallic Solids02:37

Metallic Solids

20.6K
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.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
20.6K

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Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles
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Titanium Carbene Complexes Stabilized by Alkali Metal Amides.

Hassan Osseili1, Khai-Nghi Truong1, Thomas P Spaniol1

  • 1Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.

Angewandte Chemie (International Ed. in English)
|December 15, 2018
PubMed
Summary

Light-induced alpha-H elimination from titanium precursors using alkali metal amides of the macrocyclic ligand Me3TACD yields titanium carbene complexes. These complexes exhibit nucleophilic carbene carbon atoms, reacting with benzophenone and acetylenes.

Keywords:
Wittig reactionalkali metalsalkylidenescarbenestitanium

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Photochemistry

Background:

  • Titanium complexes are versatile in catalysis and materials science.
  • Macrocyclic ligands offer unique coordination environments.
  • Photochemical reactions provide alternative synthetic pathways.

Purpose of the Study:

  • To investigate the photochemical reactivity of tetrakis(trimethylsilylmethyl)titanium precursors.
  • To explore the role of alkali metal amides and the Me3TACD ligand in titanium complex formation.
  • To characterize the resulting titanium carbene complexes and their nucleophilic properties.

Main Methods:

  • Photochemical induction of alpha-H elimination.
  • Synthesis of titanium complexes with alkali metal amides of Me3TACD.
  • Crystallographic analysis of the resulting adducts.
  • Reactions with electrophiles like benzophenone and terminal acetylenes.

Main Results:

  • Facile alpha-H elimination from titanium precursors was achieved using light and alkali metal amides of Me3TACD.
  • Adducts of (alkylidene)bis(alkyl)titanium complexes were successfully synthesized.
  • Crystallographic studies revealed alkali metal interactions with the trimethylsilylmethyl ligand.
  • The carbene carbon atom demonstrated nucleophilic character through reactions with benzophenone and terminal acetylenes.

Conclusions:

  • Alkali metal amides of Me3TACD are effective in promoting light-induced alpha-H elimination in titanium precursors.
  • The resulting titanium carbene complexes possess nucleophilic carbene centers.
  • This study expands the synthetic utility of titanium complexes and highlights the influence of macrocyclic ligands and alkali metals.