George C. Christou

Mononuclear, three-coordinate metal thiolates: Preparation and crystal structures of [NBun4][Hg(SPh)3] and [NPrn4] [Pb(SPh)3]

Abstract Dissolution of HgO or PbO in methanolic solutions of NaSPh yields homogeneous solutions from which highly crystalline [NBun4][Hg(SPh)3] (1) or [NPrn4][PB(SPh)3] (2) can be isolated on addition of appropriate quaternary ammonium salts. 1 crystallizes in monoclinic space group P21/a with a = 20.663(7), b = 16.812(6), c = 9.757(3) A, β = 95.52(2)° and Z = 4. The anion consists of a rare example of trigonal planar coordinated Hg; there are no weaker, intermolecular Hg ... S axial interactions. 2 crystallizes in triclinic space group Pl with a = 12.689(7), b = 11.255(6), c = 12.046(7) A, α = 107.93(3), β = 109.64(3), γ = 86.01(3)°, and Z = 2. The anion consists of a trigonal pyramidal coordinated PbS3 unit. The structures were solved using data collected at approx. − 160°C and refined to conventional R values of 5.7 and 4.6%, respectively for 1 and 2.