Amalgams magnetism

Chemically the iron complex 18 is reduced by K/Na alloy in THF to give a green solution of the salt 57. The d7 anion in 57 has been characterized by its ESR spectrum in frozen solution (62). Similarly, on treatment with sodium amalgam, the cobalt complexes 7 and 13 yield dark brownish-red solutions of 58 and 59, respectively. A surprisingly robust PPh4+ salt 60 (mp 158-159°C) could be isolated. Solution and solid state magnetic measurements confirm the presence of two unpaired electrons in these 20-e species as in NiCp2 (60). 

Measurements of the magnetic properties based on a selection of alkali metal rich and alkali metal poor amalgams show a different behavior at higher temperatures. 

In the glove box, 8.1 g (34.0 mmol) of freshly amalgamated uranium turnings (see Section 55.A) are placed in an oven-dried, 250-mL, one-neck Schlenk reaction vessel, along with a 1-in. Teflon-coated magnetic stirring bar, and 200 mL of distilled, degassed pyridine. The reaction vessel is removed from... 

On the otner hard,if this were the correct formula the compound should readily add bromine and reduce potassium perm ngante the first reaction it gave only in the sunlight,the other not at all1. These facts,its stability towards reduction with sodium amalgam, the value of its magnetic rotation and the fact that it behaved like a disubstltuted malonic acid4 settled the dispute in favor of Perkin. 

VO(Por) can be converted to V(Por)Cl2, by oxalyl chloride or thionyl chloride in toluene.37 The chloride has a magnetic moment of pefr = 1.62 BM and the unpaired electron (d1) is suggested to be in eg dxz, dyz) orbitals by CNDO/S MO calculations. The chloride ligands are substituted with bromide by treating V(Por)Cl2 with HBr. EXAFS study on the V(Por)Br2 revealed the V—Br bond length to be about 2.41 A. ViV(Por) is reduced by zinc amalgam in the presence of phosphine ligands... 

Most of these operations involve either amalgamation with metallic mercury, melting or fusion of the materials since the vital and spiritual energies transfer in the liquid state but they will escape if not captured by a magnet or proper medium. 

The best characterized species is [Os2(N2)(NH3)10]5+ made as a bromide or as a tosylate from reaction of [0s(H20)(NH3)s]3+ with [Os(N2)(NH3)5]2+ in the presence of zinc amalgam. The stability of the mixed valence system (formally Os111 11) has been ascribed to electronic delocalization effects and an MO scheme proposed,2 0s but it is not clear why it appears to be more stable than its reduction product, [Os(N2)(NH3),0]4+. Magnetic circular dichroism spectra and cyclic voltammetry of the ion have been measured.28011 A number of other mixed homonuclear species are known, viz. [0s2(N2)(NH3)9(H20)]s+, [Os2(N2)(NH3)9C1]4+, [Os2(N2)(NH3)8C12]3+ and... 

One of the most important reactions of diborane is its interaction with amalgams of highly active metals, e.g. sodium and potassium, to give compounds such as KgBgHg, which are sometimes referred to as salts of diborane. These compounds are non-volatile, insoluble in liquid ammonia and common organic solvents and react with water. Consequently their formulae have been determined from magnetic measurements and not from molecular weight determinations. The addition of two electrons to the electronically unsaturated diborane,... 

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