Organomercury complexes

The separation of various organomercury complexes was accomplished in RPC by including 2-mercaptoethanol in the mobile phase. This approach has been used to evaluate mercury content of fish samples (559). 

Various organomercury complexes of theophylline and theobromine have been characterized by IR, H, and 13C NMR spectroscopy <87JCR(S)186> and similar products with theophylline, 6-thioguanine and 6-thiolpurine, and caffeine were prepared <92IJC(A)972>. 

The reaction of lithiated derivatives of l,2-C2BioHi2 with mercury(II) halides is a route to organomercury complexes with Hg-Ccarbabotane bonds. " Au interesting example is shown in Scheme 3 l,2-Li2-l,2-C2BioHio reacts with HgL to give Li2[Hg4(C2BioHio)l2]. When Lil is removed, a cyclic tetrameric complex, which is described as a macrocyclic Lewis acid, is produced. 

In contrast to the situation for the 0x0 complexes discussed above, ECP-DFT calculations on shieldings in organomercury complexes indicated an... 

Alternatively, within the SOS-DFPT framework, Malkin et al. include the FC term by FPT (the SD term, which is neglected in this ansatz, has been found to be small " ). This approach has been motivated by experience with the calculation of ESR hyperfine couplings and with spin-spin coupling constants (cf. above). Based on the resulting spin-polarized Kohn-Sham orbitals, SOS-DFPT is used to account for the interplay between the external magnetic field and the spin-orbit operator. First applications include halomethanes, halomethyl cations, some other iodo compounds, and organomercury complexes. ... 

Addition of several organomercury compounds (methyl, aryl, and benzyl) to conjugated dienes in the presence of Pd(II) salts generates the ir-allylpalladium complex 422, which is subjected to further transformations. A secondary amine reacts to give the tertiary allylic amine 423 in a modest yield along with diene 424 and reduced product 425[382,383]. Even the unconjugated diene 426 is converted into the 7r-allyllic palladium complex 427 by the reaction of PhHgCI via the elimination and reverse readdition of H—Pd—Cl[383]. 

Mercuric o-carborane-l-carboxylate complexes decarboxylated when heated above their melting points or when refluxed in decane or benzene solution [Eq. (102), L = phen, bpy, or (py)2] (109,110). Asymmetric organomercury carboranes and their 1,10-phenanthroline complexes were also formed by thermal decarboxylation [e.g., Eq. (103), R = Me or Ph] (111). 

Structures of Organomercury Compounds 2.07.1.4.1 Mercury carbene and carbonyl complexes... 

Polyfunctional organomercurials have emerged as useful building blocks for the construction of supramolecular species. Compound 137, for instance, was shown to complex benzene, yielding extended binary stacks where the two components alternate (Figure 25).235 These stacks are rather compact (centroid distance of 3.24 A), so that secondary 7t-interactions occur between the benzene molecule and the mercury centers. Each of the six C-C bonds of the benzene molecule interacts with one of the six mercury centers of the two juxtaposed molecules of 137. As a result, the benzene is hexacoordinated in a fashion. The strength of the Hg-C interactions must... 

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