Jonathan G. Melnick

On the Chalcogenophilicity of Mercury: Evidence for a Strong Hg-Se Bond in [TmBut]HgSePh and Its Relevance to the Toxicity of Mercury

One of the reasons for the toxic effects of mercury has been attributed to its influence on the biochemical roles of selenium. For this reason, it is important to understand details pertaining to the nature of Hg-Se interactions and this has been achieved by comparison of a series of mercury chalcogenolate complexes that are supported by tris(2-mercapto-1-t-butyl-imidazolyl)hydroborato ligation, namely [Tm(Bu(t))]HgEPh (E = S, Se, Te). In particular, X-ray diffraction studies on [Tm(Bu(t))]HgEPh demonstrate that although the Hg-S bonds involving the [Tm(Bu(t))] ligand are longer than the corresponding Cd-S bonds of [Tm(Bu(t))]CdEPh, the Hg-EPh bonds are actually shorter than the corresponding Cd-EPh bonds, an observation which indicates that the apparent covalent radii of the metals in these compounds are dependent on the nature of the bonds. Furthermore, the difference in Hg-EPh and Cd-EPh bond lengths is a function of the chalcogen and increases in the sequence S (0.010 A) < Se (0.035 A) < Te (0.057 A). This trend indicates that the chalcogenophilicity of mercury increases in the sequence S < Se < Te. Thus, while mercury is often described as being thiophilic, it is evident that it actually has a greater selenophilicity, a notion that is supported by the observation of facile selenolate transfer from zinc to mercury upon treatment of [Tm(Bu(t))]HgSCH(2)C(O)N(H)Ph with [Tm(Bu(t))]ZnSePh. The significant selenophilicity of mercury is in accord with the aforementioned proposal that one reason for the toxicity of mercury is associated with it reducing the bioavailability of selenium.

Ligand Reactivity in Diarylamido/Bis(Phosphine) PNP Complexes of Mn(CO)3 and Re(CO)3

The syntheses of meridionally ligated tricarbonyl complexes (PNP)Mn(CO)(3) and (PNP)Re(CO)(3) are described (PNP = [2-P(CHMe(2))(2)-4-MeC(6)H(3)](2)N(-)). Cyclic voltammograms show reversible one-electron redox couples for both parent compounds (-0.34 V vs Cp(2)Fe(0/+) for (PNP)Mn(CO)(3), -0.25 V vs Cp(2)Fe(0/+) for (PNP)Re(CO)(3)), and chemical oxidation with AgOTf results in formation of the corresponding paramagnetic triflate salts [(PNP)Mn(CO)(3)]OTf and [(PNP)Re(CO)(3)]OTf. Electron paramagnetic resonance spectra and computational results indicate that this event is primarily ligand centered; allylation of the organic ligand moiety of [(PNP)Mn(CO)(3)]OTf with allyltributylstannane is consistent with this assignment. The oxidation (PNP)Mn(CO)(3) to [(PNP)Mn(CO)(3)]OTf results in a shift in average CO stretching frequency of 30 cm(-1); protonation of (PNP)Mn(CO)(3) with TfOH to form [(PNHP)Mn(CO)(3)]OTf results in a similar magnitude shift.

Synthesis, Structure, and Reactivity of Two-Coordinate Mercury Alkyl Compounds with Sulfur Ligands: Relevance to Mercury Detoxification

The susceptibility of two-coordinate mercury alkyl compounds of the type X-Hg-R (where X is a monodentate sulfur donor) towards protolytic cleavage has been investigated as part of ongoing efforts to obtain information relevant to understanding the mechanism of action of the organomercurial lyase, MerB. Specifically, the reactivity of the two-coordinate mercury alkyl compounds PhSHgR, [mim(Bu(t))]HgR and {[Hmim(Bu(t))]HgR}(+) (Hmim(Bu(t)) = 2-mercapto-1-t-butylimidazole; R = Me, Et) towards PhSH was investigated, thereby demonstrating that the ability to cleave the Hg-C bond is very dependent on the nature of the system. For example, whereas the reaction of PhSHgMe with PhSH requires heating at 145 degrees C for several weeks to liberate CH(4), the analogous reaction of PhSHgEt with PhSH leads to evolution of C(2)H(6) over the course of 2 days at 100 degrees C. Furthermore, protolytic cleavage of the Hg-C bond by PhSH is promoted by Hmim(Bu(t)). For example, whereas the reaction of {[Hmim(Bu(t))]HgEt}(+) with PhSH eliminates C(2)H(6) at elevated temperatures, the protolytic cleavage occurs over a period of 2 days at room temperature in the presence of Hmim(Bu(t)). The ability of Hmim(Bu(t)) to promote the protolytic cleavage is interpreted in terms of the formation of a higher coordinate species {[Hmim(Bu(t))](n)HgR}(+) that is more susceptible to Hg-C bond cleavage than is two-coordinate {[Hmim(Bu(t))]HgR}(+). These observations support the notion that access to a species with a coordination number greater than two is essential for efficient activity of MerB.

Monovalent indium in a sulfur-rich coordination environment: synthesis, structure and reactivity of tris(2-mercapto-1-tert-butylimidazolyl)hydroborato indium, [TmBut]In

[Tm(Bu(t))]In, the first structurally-characterized monovalent indium compound that features a sulfur-rich coordination environment, has been synthesized via treatment of InCl with [Tm(Bu(t))]K; in contrast to the thallium counterpart, the lone pair of [Tm(Bu(t))]In is a site of reactivity, thereby allowing formation of [Tm(Bu(t))]In-->B(C(6)F(5))(3) and [Tm(Bu(t))]In(kappa(2)-S(4)) upon treatment with B(C(6)F(5))(3) and S(8), respectively.

Molecular Structures of Thimerosal (Merthiolate) and Other Arylthiolate Mercury Alkyl Compounds

The molecular structure of sodium ethylmercury thiosalicylate (also known as thimerosal and Merthiolate) and related arylthiolate mercury alkyl compounds, namely PhSHgMe and PhSHgEt, have been determined by single crystal X-ray diffraction. (1)H NMR spectroscopic studies indicate that the appearance of the (199)Hg mercury satellites of the ethyl group of thimerosal is highly dependent on the magnetic field and the viscosity of the solvent as a consequence of relaxation due to chemical shift anisotropy.

Synthesis and Structural Characterization of Tris(2-seleno-1-mesitylimidazolyl)hydroborato Complexes: A New Type of Strongly Electron Donating Tripodal Selenium Ligand

A new tripodal ligand that features three selenium donors, namely the tris(2-seleno-1-mesitylimidazolyl)hydroborato ligand, [Tse(Mes)], has been constructed via the reaction of KBH(4) with 1-mesitylimidazole-2-selone; comparison of the IR spectroscopic data of [Tse(Mes)]Re(CO)(3) with those of a variety of related LRe(CO)(3) complexes demonstrates that the [Tse(Mes)] ligand is more strongly electron donating than Cp, Cp*, [Tp], [Tp(Me(2))] and [Tm(Mes)] ligands.

Methyl, hydrochalcogenido, and phenylchalcogenolate complexes of zinc in a sulfur rich coordination environment: syntheses and structural characterization of the tris(2-mercapto-1-tert-butylimidazolyl)hydroboratozinc complexes [TmBut]ZnMe, [TmBut]ZnEH (E = S, Se) and [TmBut]ZnEPh (E = O, S, Se, Te)

A series of hydrochalcogenido and phenylchalcogenolate complexes of zinc supported by tris(2-mercapto-1-tert-butylimidazolyl)hydroborato ligation, [Tm(Bu(t))]ZnEH (E = S, Se) and [Tm(Bu(t))]ZnEPh (E = O, S, Se, Te) have been synthesized from [Tm(Bu(t))]ZnMe; structural characterization by X-ray diffraction indicates that the variation in Zn-E bonding as a function of the chalcogen is significantly different from that in other series of metal-chalcogenolate compounds.

Methyl and arylchalcogenolate complexes of cadmium in a sulfur rich coordination environment: syntheses and structural characterization of the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato cadmium complexes [TmBut]CdMe, and [TmBut]CdEAr (E = O, S, Se, Te) and analysis of the bonding in chalcogenolate compounds

A series of arylchalcogenolate complexes of cadmium supported by tris(2-mercapto-1-tert-butylimidazolyl)hydroborato ligation, namely [Tm(Bu(t))]CdEAr (EAr = OC(6)H(3)Ph(2), SPh, SePh, TePh), has been synthesized from [Tm(Bu(t))]CdMe; structural characterization by X-ray diffraction indicates that the variation in Cd-EAr bond lengths is similar to that of Zn-EAr and correlates closely with the covalent radius of the chalcogen, in marked contrast to the large variation in M-OAr and M-SAr bond lengths observed for other metals (Zr and Sm).