Halides mercury compounds

There are a number of books and articles on general aspects of the coordination compounds of mercury annual surveys are published in Coordination Chemistry Reviews5 and the Annual Reports on the Progress of Chemistry, Section A (Inorganic Chemistry—Mercury).6 McAuliffe s book The Chemistry of Mercury covers the literature up to May 1975.7 The coordination chemistry of mercury(II) halides has been summarized by Dean, covering papers up to 1977.8 A review of dimercury(I) coordination compounds was published by Brodersen in 1981,9 and in the same year Grdeni6 reviewed bonding in the crystal structures of mercury compounds.10... 

Mixed halide-thiocyanate compounds Hg(SCN)X (X = Cl, Br, I) are formed from equimolar amounts of the pure components. They contain six-coordinated mercury(H) achieved by bridging X and SCN groups.234 The formation constants of the mixed thiocyanato complexes have been detected spectroscopically.233 Raman spectra of mixed halothiocyanatomercurate(U) complexes have been reported by Cooney and Hall.236 The structure of ammonium... 

The wealth of information that has accumulated regarding the UPS of the main group halides is not considered here, since it falls outside the purview of this Chapter. Of the transition metal halides the largest amount of work has been done with the halides of the Group 2B metals and their monomethyl derivatives (28, 33, 63, 108, 112, 129, 233). In these studies it was found that the zinc and cadmium dihalides require significantly higher vaporization temperatures than the mercury compounds hence specialized high-temperature techniques were necessary. A summary of these and related methods may be found in a recent review article by Schweitzer (255). 

Reversible blocking of SH groups can be obtained through the formation of unsymmetrical disulfides with a variety of sulfenyl halides, for example, 4-nitrophenylsulfenyI chloride (177), SS cleavage with trisodium phosphorothioate (178), or protection with mercury compounds such as p-mercury benzoic acid (179). In each case the free SH groups can be regenerated with mercaptans. 

Other mercury compounds suggested to be photochromic are I-Hg-S-S-Hg-I (105), the halides HgBrCl, HgICl, and HgIBr (106), and mixtures of Ag and Hgl2 (107). 

Suitable candidates for a-elimination reactions are silylmethyl halides (— base-induced elimination of H-Hal), silylmethyl dihalides (— halide/metal exchange followed by elimination of a metal halide) and stable carbenoid-type compounds such as (a-halo-a-silylalkyl)mercury compounds (— thermal elimination of mercury(II) halide). Bis(phenylthio)(trimethylsilyl)methyl lithium (— elimination of LiSPh) represents a borderline case (see Section III.E.8). 

Some applications of the use of substituted disilyl mercury compounds, Hg(SiXa)2 (X = Me,Cl), are shown in Table III there is an early review article (421). In most cases, the mercury compound reacts with a metal-halogen bond to give a silicon halide and mercury as byproduct, e.g. (entry 1),... 

Formation of inorganic silicohalides via silicohalide-mercury compounds is also possible (see Chapter 3 Silicon Halides with Si-Si Bonds) ... 

The mercury compounds HgFe(CO)4 and Fe(CO)4(HgX)2 (X = C1, Br, I), which were the first representatives of non-ionic metal derivatives of iron carbonyl hydrides, were discovered by Hock and Stuhlmann (V, 36). During investigations into the preparation of cobalt carbonyls from cobalt halides under CO pressure, in the presence of another metal as a halogen acceptor, we discovered the mixed metal carbonyls M[Co(CO)4]2 (M = Zn, Cd, Hg, Sn) and M[Co(CO)4]3 (M = In, Tl) (44), e.g.,... 

The elements form compounds R2M and RMX, where R is an alkyl or aryl group and X a halide. M C bond strengths are in the order Zn > Cd > Hg but nevertheless the mercury compounds are the most easily formed for example, from... 

In addition to mercuric sulfide itself and salts containing the HgS -ion (formed by treatment of HgS with a solution containing excess sulfide ion), four types of organic sulfur-mercury compounds might be noted (1) mercaptides of the type (RS-—)2Hg (2) halomercuri-mercapiides ( half halide, half mereaptide ) of tyue X—Hg—SR (3) sulfide adducts of the... 

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