Mercury-nitrogen complexes

The oxidation probably involves a mercurated complex through the electron pair on nitrogen followed by a concerted removal of a proton from the a-carbon and then cleavage of the mercury-nitrogen bond. The suggestion that a trans elimination occurs is reinforced by the evidence that yohimbine can be hydrogenated by mercuric acetate, whereas reserpine methyl reserpate, deserpine, or pseudoyohimbine does not react [122]. 

Summarizing, these mercury-nitrogen compounds provide examples of all four types of Hg-N complex, namely ... 

Mercury(I) forms few complexes, one example is the linear [H2O-Hg Hg- H20] found in the mercury(I) nitrate dihydrate (above, p. 437), In contrast, mercury(II) forms a wide variety of complexes, with some peculiarities (a) octahedral complexes are rare, (b) complexes with nitrogen as the donor atom are common, (c) complexes are more readily formed with iodine than with other halogen ligands. 

The possible structures for isothiazoles are discussed in Section 4.01.1, and attention in this chapter will be directed mainly towards the aromatic systems, as defined in Section 4.01.1. The saturated isothiazole 1,1-dioxides (5) are known as sultams, and bicyclic compounds of structure (6) are called isopenems. Isothiazoles readily coordinate to metals (76MI41703, 78MI41701, 79MI41700, 80MI41701). Coordination usually takes place through the nitrogen atom, but sulfur coordination can occur with soft metals such as cadmium or mercury. Some specific coordination complexes are discussed in later sections. 

The bicyclic amine 11-methyl-l l-azabicyclo[5.3.1]hendecanc (71) provided a model system in which the hydrogens on the equivalent a-tertiary-carbon atoms cannot be trans to the nitrogen-mercury bond in the mercur-ated complex and in which epimerization at these a carbons is impossible (77). This bicyclic system is large enough to accommodate a... 

The most general method for synthesis of cyclic enamines is the oxidation of tertiary amines with mercuric acetate, which has been investigated primarily by Leonard 111-116) and applied in numerous examples of structural investigation and in syntheses of alkaloids 102,117-121). The requirement of a tram-coplanar arrangement of an a proton and mercury complexed on nitrogen, in the optimum transition state, confers valuable selectivity to the reaction. It may thus be used as a kinetic probe for stereochemistry as well as for the formation of specific enamine isomers. 

Mercury has a characteristic ability to form not only conventional ammine and amine complexes but also, by the displacement of hydrogen, direct covalent bonds to nitrogen, e.g. ... 

Amino-3-methyl-5-thione-l,2,4-triazole with [HgR(MeCOO)] (R = Me, Ph) gives complexes 186, where coordination occurs via the sulfur and amino nitrogen atoms (93JOM(450)41). In the crystalline state, intermolecular interaction of the mercury site with the endocyclic nitrogen atom of the neighboring unit is also observed. 

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. 

The solution should be free from the following, which either interfere or lead to an unsatisfactory deposit silver, mercury, bismuth, selenium, tellurium, arsenic, antimony, tin, molybdenum, gold and the platinum metals, thiocyanate, chloride, oxidising agents such as oxides of nitrogen, or excessive amounts of iron(III), nitrate or nitric acid. Chloride ion is avoided because Cu( I) is stabilised as a chloro-complex and remains in solution to be re-oxidised at the anode unless hydrazinium chloride is added as depolariser. 

S.2.4.2.3. Complexes of Mercury(l) with Nitrogen-Donor Ligands. 

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