Synthesis of luminescent zirconium thiolate complexes. Crystal structures of (η5-C5H5)2Zr(SC6H4Cl-p)2 and [(η5-C5H5)2Zr(SC6H4OMe-p)]2O

Article abstract of DOI:10.1016/s0022-328x(97)00488-9

Several luminescent zirconium thiolate complexes (η₅-C₅H₅)₂Zr(SC₆H₄R-p)₂, where R = Cl (1), Me (2), OMe (3), have been synthesized by the reaction of Cp₂ZrCl₂ with HSC₆H₄R-p in the presence of Et₃N. The crystal structures of (η⁵-C₅H₅)₂Zr(SC₆H₄Cl-p)₂ and [(η⁵-C₅H₅)₂Zr(SC₆H₄OMe-p)]₂O (4), which has been isolated as a hydrolysis product of (η⁵-C₅H₅)₂Zr(SC₆H₄OMe-p)₂, have been determined. Complex 1 crystallizes in the monoclinic space group P2₁/a, with a = 12.182(1) A?, b = 10.674(4) A?, c= 17.131(2) A?, β= 103.949(6)°, Z = 4, and V = 2161.8(6) A?³. The Zr atom is in a distorted tetrahedral coordination environment with the thiolate ligands adopting an endo(anti) configuration. The two Cp rings have a nearly eclipsed geometry. Complex 4 crystallized in the monoclinic space group P2₁/c, with a= 15.533(1) A?, b = 15.217(4) A?, c = 13.382(2) A?, β = 90.00(2)°, Z = 4, and V = 3162(1) A?³.