Ferrocene-mercury complexes

Scheme 7-45 shows a series of l,l -bis(diphenylphosphino)ferrocene-mercury complexes, to which a tetrahedral geometry has been assigned [151, 204, 207],... 

Interaction of iron(II) chloride with the lithium salt of R4B2NJ (R = Me, Et) gives sandwiches 61 (R = Me, Et) (67ZAAC1, 96MI4), resembling in electronic properties those of ferrocene (99ICA(288)17). The n- rf-) complex stems from the further complex-formation of 61 (R = Me, Et) with mercury(II) salts via the unsubstituted nitrogen atom. 

With tetracarbonyliron, mercury tetracarbonylferrate(II), ferrocene or dicarbonyl-cyclopentadienyliron, imidazole forms iron(II) complexes of the general form Fe(C3H3N2)2 or Fe(C3H3N2)2 0.5(C3H4N2). Iron(III) complexes have also been described. 

The colorless zinc compound, Zn(CisH6)2, which sublimes at 160° under partial decomposition, is obtained in small yield from zinc chloride and cyclopentadienyl sodium in diethyl ether however, the less stable cadmium compound decomposes, with separation of cadmium, under these conditions (55). The mercury compound, Hg(CsH5)2, is produced in 20% yield by the action of the sodium derivative on mercuric chloride in tetrahydrofuran (215). The action of cyclopentadiene on the complex K2(HgI ) in aqueous alkaline solution results in the precipitation of a mixture of CsHsHgl and Hg(CsH6)2, from which the latter compound may be obtained in good yield by extraction with a mixture of tetrahydrofuran and petroleum ether (62). It forms pale yellow crystals which begin to decompose at about 60° and which melt at 83-85°. The compound is readily soluble in most solvents it decomposes slowly even when kept in the dark at room temperature it is insoluble in water and reacts with neither water nor bases. On the other hand, decomposition occurs in dilute hydrochloric acid. It converts ferric chloride to ferrocene quantitatively, and it yields an adduct with maleic anhydride (215). 

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