Mercury(II) 2-aminoethanethiolate clusters: intramolecular transformations and mechanisms.
The combination of HgF2 and 2-aminoethanethiol (AET, with some AET.HCl present) yielded a cyclic tetranuclear thiolate, [Hg4Cl4(SCH2CH2NH2)4] (1), with alternating Hg and S atoms. The Cl from the reaction mixture led to the formation of Hg-Cl bonds with no Hg-F in the final product. In contrast, a similar reaction with HgBr2 yielded a nonanuclear cluster, [Hg9Br15(SCH2CH2NH3)15]3+ (2), and the disulfide salt {[HgBr4][(NH3CH2CH2S-)2]} (3). Despite similar reactions, the AET groups in 2 are protonated compared to the nonprotonated amine groups in 1, which allows the ligand to chelate the Hg atom in the latter compound. The reaction with HgI2 yielded a cyclic tetranuclear compound, [Hg4I6(SCH2CH2NH2)2(SCH2CH2NH3)2](H2O/EtOH) (4), containing protonated and nonprotonated AET groups. Compound 4 at room temperature irreversibly rearranges to [Hg4I4(SCH2CH2NH2)4] (5), which is isostructural to 1. A systematic pathway for the formation of 1 along with the intramolecular conversion of 4 to 5 is proposed. These compounds demonstrate that very diverse Hg-S compounds form under similar reaction conditions.
Bharara
Mohan S
MS
Department of Chemistry, University of Kentucky, Lexington, KY 40506-006, USA.
Parkin
Sean
S
Atwood
David A
DA
D018360:Crystallography, X-Ray; D003543:Cysteamine / Q000737:chemistry*; D008628:Mercury / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009941:Organomercury Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D009941:Organomercury Compounds; D003543:Cysteamine; D008628:Mercury