Silyl complexes with mercury

Silylation of Salts of AN a-Functionalized AN 52a-c (trinitro-methane, dinitroethane, dimethyl nitromalonate, nitroacetates, etc.) can form salts, which are quite stable. It should be noted that stability of silver and mercury salts can be increased by complexation with neutral molecules (e.g., with dioxane). Hence, for these AN it is advantageous to prepare salts A, which react with halosilanes to smoothly form the corresponding SENAs 51a—C (Scheme 3.51) (174-177). 

The first mercury(I) silyl complex [(Me3SiMe2Si)3Si]2Hg2 was prepared by the reaction of an excess of (Me3SiMe2Si)3SiH with (t-Bu)2Hg. The solid structure of the complex displays linear Si—Hg—Hg—Si fragment with regular metal-silicon bond lengths... 

Transition metal carbodiimides, such as MnNCN and CuNCN, and carbodiimides derived from zinc, mercury,silver and thallium are also known. A preceramic polymeric titanium carbodiimide is obtained in the reaction of TiCU with bis(trimethyl-silyl)carbodiimide. Liganded carbodiimidotitanium complexes are obtained in the reaction of CpaTiCla with Me3SnN=C=NSi(i-Pr)3. ° Also, dicyclopentadienyl titanium (IV) diisocyanates are converted into carbodiimides with LiN(SrMe3)2. ... 

Desulphurisation of a diphosphine sulphide by heating with a metal is another good method (Figure 9.24), and in some circumstances P-N linkages can be replaced by P-P (6.664). Diphosphines are also formed from silyl phosphines (Figure 9.10) and by disproportionation of dimethylphosphi-nous fluoride (6.175) and of more complex phosphines. An uncommon reaction is the decomposition of mercury ter-butyl phosphide by ultraviolet radiation in benzene solution (6.665). At low temperatures some unsymmetrical derivatives can be formed (6.666). 

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