Ligands solid state reactions

A re-investigation of the complex [Pd(en)(enH)Cl]Cl2,H20 has confirmed this formulation containing a protonated ethylenediamine ligand. In addition, the complex was observed to undergo a facile solid-state reaction ... 

Quite a number of interesting solid-state reactions have been observed that do not quite fit into the categories of earlier sections. These include reactions of coordinated ligands, changes of coordination number or geometry and polymerization reactions. Limitations of space do not permit detailed discussions of these reactions. 

In cases where substitutions are extremely slow, high-temperature solid-state reactions can sometimes provide a convenient and efficient means of exchanging outer cluster ligands. Melts of ionic compounds with an anionic component that... 

One problem is that coordinated oxygen oxidizes the tertiary phosphine ligands to form free tertiary phosphine oxide. Often the course of this reaction is solvent dependent in ethanol the phosphine oxide is more likely to be formed than in hydrocarbon solvents.945 The oxidation of ligands also occurs in the solid state reaction.942... 

As noted above, the ability of ligands with multiple phenyl rings positioned to allow resonance stabilization in an anion makes them ideal candidates for DAIP. Recent reports have demonstrated this with the presentation of a family of heavy alkaline earth triphenyhnethanides, all of which occur as charge-separated complexes in the solid state. Reaction of dibenzylbarium or strontium with triphenylmethane in the presence of 18-crown-6 and HMPA leads to the isolation of the DAIP triphenylmethanide, the barium compound of which is shown in Figure 35. 

In the meantime, homoatomic ligand-free Zintl clusters of tetrel atoms are known for compositions [ 4 , [ 5] , and [ g] with = Si, Ge, Sn, Pb and n = 2-4. A unique example of a cluster with ten vertices is [Pbio] with a bicapped quadratic anti-prismatic structure (Figure 3.1). The smallest clusters [ 4]" were first prepared in solid-state reactions of alkali metals (A = Na, K, Rb, Cs) with elemental tetrels ( = Si, Ge, Sn, Pb) in a 1 1 ratio [8]. 

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