The transmetalation reaction of Hg(SPy)2 (SPy = S-2-NC5H4) with Eu in pyridine gives the europium(II) pyridinethiolate coordination complex (py)4Eu(SPy)2 (1) in 96% isolated yield. The reaction of 1 with BIPY in THF results in displacement of the pyridine ligands and the formation of the divalent coordination complex (BIPY)-(THF)2Eu(SPy)2 (2). Low-temperature single-crystal X-ray diffraction experiments show that 1 and 2 are molecular 8 coordinate compounds. They are both intensely colored due to the presence of a visible europium-to-pyridine or europium-to-BIPY charge transfer (CT) absorption band. Trivalent [PEt4][Eu(SPy)4] (3) was prepared from the reaction of Eu/Hg amalgam with PySSPy in the presence of [PEt4[SPy]. X-ray diffraction analysis of 3 shows that all the pyridinechalcogenolate ligands are chelating the Eu(III) ion and there are three different eight coordinate isomers within the unit cell. Compound 3 is intensely colored because of a visible S-to-Eu CT absorption. At 500°C, 3 decomposes to give EuS and a mixture of PySSPy, PySPy, EtSPy, and SPEt3. Crystal data (Mo Ka, 153(5) K): 1, orthorhombic space group Pna2/1, a = 19.006(2) Å,b = 9.724(5) Å, c = 15.592(5) Å, Z = 4; 2, monoclinic space group Cc, a = 9.851(2) Å,b= 16.817(3) Å, c = 17.271(2) Å, β = 92.67(2)°, Z = 4; 3, monoclinic space group P21/n, a = 15.043(3) Å,b= 16.036(6) Å, c = 26.444(5) Å, β = 90.54(2)°, Z= 4.
All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
- Physical and Theoretical Chemistry