TY - JOUR
T1 - Mercury(II) 2-aminoethanethiolate clusters
T2 - Intramolecular transformations and mechanisms
AU - Bharara, Mohan S.
AU - Parkin, Sean
AU - Atwood, David A.
PY - 2006/9/4
Y1 - 2006/9/4
N2 - The combination of HgF2 and 2-aminoethanethiol (AET, with some AET·HCl present) yielded a cyclic tetranuclear thiolate, [Hg 4Cl4(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(SCH2CH2NH 3)15]3+ (2), and the disulfide salt {[HgBr 4][(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 Hgl2 yielded a cyclic tetranuclear compound, [Hg4I6(SCH2CH 2NH2)2(SCH2CH2NH 3)2](H2O/EtOH) (4), containing protonated and nonprotonated AET groups. Compound 4 at room temperature irreversibly rearranges to [Hg4I4(SCH2CH2NH 2)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.
AB - The combination of HgF2 and 2-aminoethanethiol (AET, with some AET·HCl present) yielded a cyclic tetranuclear thiolate, [Hg 4Cl4(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(SCH2CH2NH 3)15]3+ (2), and the disulfide salt {[HgBr 4][(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 Hgl2 yielded a cyclic tetranuclear compound, [Hg4I6(SCH2CH 2NH2)2(SCH2CH2NH 3)2](H2O/EtOH) (4), containing protonated and nonprotonated AET groups. Compound 4 at room temperature irreversibly rearranges to [Hg4I4(SCH2CH2NH 2)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.
UR - http://www.scopus.com/inward/record.url?scp=33748792002&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33748792002&partnerID=8YFLogxK
U2 - 10.1021/ic060863e
DO - 10.1021/ic060863e
M3 - Article
C2 - 16933927
AN - SCOPUS:33748792002
SN - 0020-1669
VL - 45
SP - 7261
EP - 7268
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -