Magnesium ammonia complex

R)-ex-(rm-Butyldimethylsilyloxy)benzeneacetonitrile was allowed to react with methyl-magnesium iodide to form an imine intermediate. The imine-magnesium complex was converted into the free imine and treated with an excess of an alkylamine (methylamine. benzylaminc. 2-phenylethylamine) to give, with loss of ammonia, the secondary imine. Reduction with sodium borohydride afforded the rerf-butyldimethylsilyloxy-protected A-alkylethanolamines in yields of92-98%. As already known from previous work7 8, these reductions proceed with excellent diastereoselectivity9. 

This colour change can be observed with the ions of Mg, Mn, Zn, Cd, Hg, Pb, Cu, Al, Fe, Ti, Co, Ni, and the Pt metals. To maintain the pH constant (ca 10) a buffer mixture is added, and most of the above metals must be kept in solution with the aid of a weak complexing reagent such as ammonia or tartrate. The cations of Cu, Co, Ni, Al, Fe(III), Ti(IV), and certain of the Pt metals form such stable indicator complexes that the dyestuff can no longer be liberated by adding EDTA direct titration of these ions using solochrome black as indicator is therefore impracticable, and the metallic ions are said to block the indicator. However, with Cu, Co, Ni, and Al a back-titration can be carried out, for the rate of reaction of their EDTA complexes with the indicator is extremely slow and it is possible to titrate the excess of EDTA with standard zinc or magnesium ion solution. 

Ammonia fails to act as an effective nucleophile for 7r-allylpalladium complexes. Some examples of primary amines81-181-183 have been reported, although diallylation is often a problem in these reactions. Secondary amines are, however, excellent substrates for palladium-catalyzed allylation.81-84,181-183-195 Amides,176-196 sulfonamides,196-197 azides198 and magnesium amides199 have also been shown to be effective nucleophiles. 

Anhydrous hydrazine dssolves many salts, thus, 100 parts of solvent at 12-5°-13° dissolve 12-2 parts of sodium chloride 8 5, of potassium chloride 56-4, of potassium bromide 135-7, of potassium iodide 26-6, of sodium nitrate 21-7, of potassium nitrate and 814, of barium nitrate. The hydrazine seemed to unite with sodium chloride with a warm soln. of ammonium chloride, ammonia is evolved, and in the cold, there seems to be a state of equilibrium a complex salt seems to be formed with lead nitrate. An aq. soln. of hydrazine hydrate also dissolves a number of salts, potassium bromide and iodide, ammonium sulphate, potassium cyanide, barium nitrate, magnesium sulphate, etc. According to T. W. B. Welsh and H. J. Broderson, the solubility of the metal haloids seems to... 

Ammonia and alkyl amines do not form complexes in aqueous solution, but the solid halides can give adducts of the type MC12-hNH3 and magnesium halides give complexes such as MgBr2py4. 

We found these conditions by introducing surface-active materials to a solution of a specially prepared catalytic complex containing molybdenum and stabilized by magnesium ions [22]. The structure of the complex which was isolated from the solution in its oxidized form is presented on Figure 5 [23]. When it is reduced to the Mo state the complex becomes an active catalyst of dinitrogen reduction to hydrazine and ammonia by sodium amalgam. Phospholipid (phosphatidylcholine)... 

---