Metal Chloride Reductions with Aromatic Radical Anions. The Magnesium Chloride Catalysed Cleavage of Tetrahydrofuran by Sodium Naphthalene Radical Anion

2007 ◽  
Vol 72 (5-6) ◽  
pp. 589-598
Author(s):  
Barry R. Steele ◽  
Georgios A. Heropoulos ◽  
Constantinos G. Screttas
Keyword(s):  
Alkali Metal ◽  
Organic Synthesis ◽  
Magnesium Chloride ◽  
Radical Anion ◽  
Catalytic Amount ◽  
Metal Chloride ◽  
Metal Salts ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Metallic Magnesium

Activated metals for organic synthesis are often prepared by reduction of metal salts using alkali metal aromatic radical anions. The reduction of magnesium chloride has been examined by NMR. Whereas the expected reduction to the metal occurred with lithium or potassium naphthalene radical anion, under certain conditions, with sodium naphthalene radical anion, no metallic magnesium was precipitated and dark red solutions were obtained. It was also found that solutions of sodium naphthalene radical anion in tetrahydrofuran, in the presence of a catalytic amount of magnesium chloride, quickly became diamagnetic. A mechanism involving bimetallic species is postulated to explain the results.

Raman spectroscopic studies of structural properties of solid and molten states of the magnesium chloride – alkali metal chloride system

1980 ◽  
Vol 58 (2) ◽  
pp. 168-179 ◽  
Author(s):  
M. H. Brooker ◽  
C.-H. Huang
Keyword(s):  
Phase Diagram ◽  
Raman Spectrum ◽  
Alkali Metal ◽  
Structural Properties ◽  
Magnesium Chloride ◽  
Spectroscopic Studies ◽  
Metal Chloride ◽  
Alkali Metal Chloride ◽  
Chloride System ◽  
Raman Spectroscopic

Raman spectra have been recorded for solids and melts of composition MgCl2 + nACl (n = 0–4 and A = Cs, Rb, K, Na, Li). Characteristic spectra have been observed for each of the solids predicted from phase diagram studies and an additional two compounds formulated as Rb3MgCl5 and K3MgCl5 were detected. The compounds Cs2MgCl4, Cs3MgCl5, and Rb3MgCl5 contain the discrete MgCl42− tetrahedral ion which has been characterized by its Raman spectrum. These compounds melt with retention of the MgCl42− ion. Most other solids appear to contain distorted network octahedra with face-, edge-, or corner-shared chlorides. These solids melt to give the more stable tetrahedral MgCl42− ion. In melts of high MgCl2 concentration a new peak was detected which appears to be characteristic of the dimeric Mg2Cl73− ion which exists in equilibrium with the MgCl42− ion. The results are compared to similar studies on the better characterized CsCl–AlCl3 system.

Design, synthesis and isolation of a new 1,2,5-selenadiazolidyl and structural and magnetic characterization of its alkali-metal salts

2019 ◽  
Vol 43 (41) ◽  
pp. 16331-16337
Author(s):  
Nikolay A. Semenov ◽  
Ekaterina A. Radiush ◽  
Elena A. Chulanova ◽  
Alexandra M. Z. Slawin ◽  
J. Derek Woollins ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Alkali Metal ◽  
Electron Acceptor ◽  
Radical Anion ◽  
Metal Salts ◽  
Alkali Metal Salts ◽  
Magnetic Characterization ◽  
Design Synthesis

A new electron acceptor is synthesized and reduced into its radical-anion isolated in the form of two salts with different structures and magnetic properties.

Fragmentation Rates of Aromatic Radical Anions and the π*— σ* Orbital Crossing Point

1984 ◽  
Vol 39 (1) ◽  
pp. 49-54 ◽  
Author(s):  
H. O. Villar ◽  
E. A. Castro ◽  
R. A. Rossi
Keyword(s):  
Carbon Atom ◽  
Molecular Orbital ◽  
Qualitative Agreement ◽  
Radical Anion ◽  
Reaction Coordinate ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Orbital Crossing ◽  
Crossing Point

The reaction coordinate of the fragmentation of aromatic radical anions with nucleofugal groups was studied by the INDO and MNDO techniques. The reaction coordinate turned out as the stretching between the nucleofugal group bonded to the carbon atom of the aryl moiety. It was found that to fragment a π* radical anion, the odd electron has to be transferred to the σ* molecular orbital of the aryl-nucleofugal bond by an orbital crossing, which is reached by the lengthening of this bond. There is a qualitative agreement between the length of the bond to reach the orbital crossing point and the experimental fragmentation rates of the aromatic radical anions. Finally, some considerations about the σ-π coupling are made, since it is defining the possibility of a transfer from the π* to the σ* molecular orbital.

On the Dissociation of Aromatic Radical Anions in Solution. 1. Formulation and Application top-Cyanochlorobenzene Radical Anion

2003 ◽  
Vol 107 (51) ◽  
pp. 11271-11291 ◽  
Author(s):  
Damien Laage ◽  
Irene Burghardt ◽  
Thomas Sommerfeld ◽  
James T. Hynes
Keyword(s):  
Radical Anion ◽  
Radical Anions ◽  
Aromatic Radical
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