Mercury II ions

It is a colourless gas which decomposes on heating above 420 K to give metallic tin, often deposited as a mirror, and hydrogen. It is a reducing agent and will reduce silver ions to silver and mercury(II) ions to mercury. SnSn bonding is unknown in hydrides but does exist in alkyl and aryl compounds, for example (CH3)3Sn-Sn(CH3)3. 

Mercury(II) oxide, HgO, occurs in both yellow and red forms the yellow form is precipitated by addition of hydroxide ion to a solution containing mercury(II) ions, and becomes red on heating. Mercury(II) oxide loses oxygen on heating. 

C = C triple bonds are hydrated to yield carbonyl groups in the presence of mercury (II) ions (see pp. 52, 57) or by successive treatment with boranes and H2O2. The first procedure gives preferentially the most highly substituted ketone, the latter the complementary compound with high selectivity (T.W. Gibson, 1969). 

The acid promoted cyclization of AT-(2-chloroallyl)enaminones (Scheme 35a) provides the expected 3-methyltetrahydroindoles, whereas similar treatment of iV-(2-chloroallyl)anilines yields unexpectedly 2-, rather than 3-, methylindoles (Scheme 35b) (75JCS(Pl)U46). The course of the latter cyclization is not resolved although various intermediates, such as those shown, have been considered. The ring closure in the furan synthesis shown in Scheme 35c is catalyzed by mercury(II) ion (79JCs(Pl)316l). 

Like alkenes (Sections 7.4 and 7.5), alkynes can be hydrated by either of two methods. Direct addition of water catalyzed by mercury(II) ion yields the Markovnikov product, and indirect addition of water by a hydroboration/ oxidation sequence yields the non-Markovnikov product. 

O The alkyne uses a pair of electrons to attack the electrophilic mercury(II) ion, yielding a mercury-containing vinylic carbocation intermediate. 

Discussion. Silver can be extracted from a nearly neutral aqueous solution into nitrobenzene as a blue ternary ion association complex formed between silver(I) ions, 1,10-phenanthroline and bromopyrogallol red. The method is highly selective in the presence of EDTA, bromide and mercury(II) ions as masking agents and only thiosulphate appears to interfere.8... 

Determination. To an aliquot of the silver(I) solution containing between 10 and 50 pg of silver, add sufficient EDTA to complex all those cations present which form an EDTA complex. If gold is present (>250 xg) it is masked by adding sufficient bromide ion to form the AuBr4 complex. Cyanide, thiocyanate or iodide ions are masked by adding sufficient mercury(II) ions to complex these anions followed by sufficient EDTA to complex any excess mercury(II). Add 1 mL of 20 per cent ammonium acetate solution, etc., and proceed as described under Calibration. 

The standard potentials [ns N.H.E. (see Section 2.28)] of the fundamental couples involving uncomplexed mercury(I) and mercury(II) ions are ... 

Rate law and mechanism. Suggest one reaction scheme for the oxidation of vana-dium(III) ions by mercury)II) ions on the basis of the rate equation given. 

What volume (in liters) of a saturated mercury(Il) sulfide, HgS, solution contains an average of one mercury(II) ion, Hg2+ ... 

Anthraquinone-1-sulphonic acid is the traditional precursor of 1-aminoanthraquinone (6.8), the most important anthraquinone intermediate. Since it is expensive to eliminate mercury(II) ions from waste water, an alternative route via 1-nitroanthraquinone has been investigated. Nitration of anthraquinone gives, as well as the desired 1-nitro derivative, significant amounts of the 2-isomer together with 1,5- and 1,8-dinitroanthraquinones. Nevertheless, chemists at Sumitomo in Japan have optimised the nitration procedure with respect to both yield and purity of the 1-nitro compound. In particular, nitration is stopped when 80% of the anthraquinone has been substituted [5]. Nitration of anthraquinone derivatives is also of some significance. 

Liu CW, Huang CC, Chang HT et al (2009) Highly selective DNA-based sensor for lead(II) and mercury(II) ions. Anal Chem 81 2383-2387... 

It is noteworthy that a complete stereoselectivity toward the cA-isomer, which is opposite to that found in aminomercuration of the same dienes173 characterizes these reactions. The following mechanism has therefore been proposed to rationalize the stereochemical behavior. After the addition to one of the double bonds, the electron pair of the nitrogen should interact with the mercury atom. In a second step, another mercury(II) ion from an additional molecule of mercury(II) nitrate is similarly complexed by the electrons of the nitrogen atom, requiring an approach from that same side and resulting in a cis... 

Write the net ionic equation and the half-reactions for the disproportionation of mercury(I) ions in aqueous solution to give liquid mercury and aqueous mercury(II) ions. Assume that mercury(I)... 

In this connexion it should also be noted that the hydrated mercury (II) ion is an octahedral hydrate with six equivalent Hg-0 bonds, presumably of a fairly ionic character (79). Upon hydrolysis, two of these bonds are shortened from just over 2.3 A to 2.0—2.1 A, so that a linear group O—Hg—O is formed. The bonds within this group are evidently much stronger than the original ones and fairly covalent. The remain-... 

In the original German process acetylene is injected into an aqueous solution of mercuric sulfate acidified with sulfuric acid at 90-95°C and about 1-2 atm. As a result of side reactions, the catalytically active mercury(II) ions are reduced to mercury. To prevent this process ferric sulfate is continuously added to the reactor. Since ferric ions are reduced to ferrous ions, the catalyst solution requires reactivation, which is accomplished by hot nitric acid and air. Excess acetylene and acetaldehyde formed are removed, cooled, absorbed in water, and then separated by distillation. Excess acetylene is recycled. Conversion per pass is bout 55%. The Montecatini process89 operates at 85°C and provides 95% overall yield. A modification developed by Chisso90 allows lower operating temperature (70°C) without excess acetylene. Since side reactions are less important under these conditions, higher yields may be achieved. 

Crosslinked polymers of vinyl-substituted imidazolecarboxylic acids have been studied as chelating resins for heavy metal ions (78MI11101). For example, polymer (75) displays stabilities and capacities in the order Cu2+ > Ni2+ > Cd2+ > Zn2+ > Mg2+ which is similar to that observed with other amino acid chelating resins. The unusual feature of the polymer, however, is that exceptionally strong complexing abilities are maintained even in strongly acidic media. Polymer (75) also displayed potential utility for the removal of mercury(II) ions from aqueous media. 

R. J. Ferrier and S. R. Haines, Alkenes from 4-bromohexofuranose esters reactions of 5-deoxyald-4-enofuranose derivatives in the presence of mercury(II) ions, J. Chem. Soc. Perkin Trans. 1 1689 (1984). 

Enol lactones with a halogen at the vinylic position have been synthesized as potential mechanism-based inactivators of serine hydrolyases <81JA5459). 5-Hexynoic acids (181) can be cyclized with mercury(II) ion catalysis to y-methylenebutyrolactones (182) (Scheme 41). Cyclization of the 6-bromo and 6-chloro analogues leads stereospecifically to the (Z)-haloenol lactones (trans addition) but is quite slow. Cyclization of unsubstituted or 6-methyl or 6-trimethylsilyl substituted 5-hexynoic acids is more rapid but alkene isomerization occurs during the reaction. Direct halolactonization of the 5-hexynoic acids with bromine or iodine in a two-phase system with phase transfer catalysis was successful in the preparation of various 5-halomethylene- or 5-haloethylidene-2-phenylbutyrolactones and 6-bromo-and iodo-methylenevalerolactones (Scheme 42). 

Mercury (II) ions can add in place of H+ in the first step of Eq. 15-20 and subsequent reactions similar to those promoted by acid can occur.137... 

By comparison with the mercury(I) and mercury(II) ions (Chapter 56.1), the coordination chemistry of (10) and (11) has received little attention. Both ions disproportionate to Hg° and Hg2+ /Hg2+ in media more basic than those from which they can be prepared. However, the existence of (11) (which can be regarded as a complex of (10) with Hg°) and the cation-anion coordination found in solid salts of (10)38 suggest that this ion, at least, might form stable complexes with suitable weak donors. In addition, the formation of as yet incompletely characterized Hg2BrCI04 2SnBr2, which may contain both Hg—Hg and Hg—Sn bonds,42 and the isolation and characterization of [ (np3)Co HgHg Co(np3) ] (1 see Section 11.2) may presage a wider occurrence of catenated heterometallic polymercury species. Slow disproportionation of (11) into (10) and Hg3-X(MF6) occurs even in liquid S02.39 As discussed below, there is evidence for mercury atom transfer between (10) and (11) in liquid S02. 

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