Mercury coordination chemistry of a nitrogen/thioether sulfur ligand having an internal hydrogen bond donor: Generation of a thioether-coordinated dimercurous complex
Issue title: Special Issue based on the Symposium: Main Group Chemistry: A Continual Source of Fundamental New Knowledge and Applications in Everyday Life; 67th Southwest Regional Meeting of the American Chemical Society Austin, TX, USA; November 9–12, 2011 Guest Editor: John C. Gordon
Affiliations: Department of Chemistry and Biochemistry, Utah State University, Logan, UT, USA | Department of Chemistry, College of William and Mary, Williamsburg, VA, USA | Department of Chemistry, University of Utah, Salt Lake City, UT, USA
Note: [] Corresponding author: Lisa M. Berreau, Department of Chemistry and Biochemistry, Utah State University, Logan, UT, USA. Tel.: +1 435 797 3509; Fax: +1 435 797 3390; E-mail: [email protected]
Abstract: Admixture of the chelate ligand bmnpa (N,N-bis(2-methylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine) with an equimolar amount of Hg(ClO4)2·3H2O in CH3OH/CH2Cl2, followed by recrystallization from CH3CN/Et2O, yielded the Hg(II) perchlorate complex [(bmnpa)Hg(ClO4)2] (1). Addition of an equimolar amount of Me4NOH·5H2O to a CH3CN solution of 1, followed by recrystallization from CH3OH/Et2O, yielded the dinuclear Hg22+ complex [(bmnpaHg)2](ClO4)2 (4). X-ray crystallographic characterization of 1·0.5CH3CN revealed a mononuclear structure having a primary coordination number of two with a distorted linear geometry, and four secondary bonds for an effective coordination number of six. The 1H NMR spectrum of 1 in CD3CN shows distinctive 3J199Hg-1H coupling in the benzylic -CH2- and thioether -SCH3 resonances. Complex 4·CH3OH exhibits a structure in the solid state wherein each mercury center of the Hg22+ ion displays thioether coordination and a distorted tetrahedral geometry. Complex 4 is the first dimercurous complex for which J199Hg-1H coupling involving a -SCH3 appendage is reported.
