Heterometallic Eu/M(II) Benzenethiolates (M = Zn, Cd, Hg): Synthesis, Structure, and Thermolysis Chemistry

Article abstract of DOI:10.1021/ic00127a033

Europium-mercury amalgam reacts with diphenyl disulfide in THF to give a heterometallic product that crystallizes from pyridine (py) as [(py)3Eu(μ2-SPh)2(μ3-SPh)Hg(SPh)]2.2py (1). Cluster 1 reacts with Cd in pyridine to give [(py)3Eu(μ2-SPh)2(μ3-SPh)Cd(SPh)]2.2py (2) and with Zn in THF to give [(THF)3Eu(μ2-SPh)2(μ3-SPh)Zn(SPh)]2.THF (3). All three compounds have been characterized by NMR, IR, and UV-visible spectroscopy and by single-crystal X-ray diffraction. The three are structurally related; 1 and 2 are isostructural tetrametallic clusters with μ2 and μ3 thiolate ligands connecting the 7-coordinate Eu(II) and tetrahedral group 12 metal ions. The lanthanide coordination sphere is saturated with three neutral pyridine donors, and the group 12 metal ion isbound to a terminal benzenethiolate ligand. The zinc cluster 3 has the same tetrametallic framework and connectivity as 1 and 2 but crystallizes in a different unit cell. The thermolysis products of these compounds have been established: 1 decomposes to give EuS, Ph2S, Hg, and S2Ph2; 2 eliminates Ph2S to give a mixture of CdS and EuS; 3 eliminates Ph2S to give a mixture of EuS and ZnS. Crystal data for 1-3 (Mo Kα radiation, -100°C): 1, triclinic space group P1-, a = 13.954(3) ?, b = 15.311(4) ?, c = 19.666(8) ?, α = 84.54(3)°, β = 86.40(3)°, γ = 87.25(3)°, Z= 2; 2, triclinic space group P1-, a = 13.968(3) ?, b = 15.387(6) ?, c = 19.993(8) ?, α = 84.74(3)°, β = 86.21(3)°, γ = 87.30(3)°, Z = 2; 3, monoclinic space group P21/n, a = 13.920(5) ?, b = 17.049(5) ?, c = 17.823(6) ?, β = 103.7(3)°, Z = 4.