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

Abstract

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) Å, b = 10.674(4) Å, c= 17.131(2) Å, β= 103.949(6)°, Z = 4, and V = 2161.8(6) Å3. 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) Å, b = 15.217(4) Å, c = 13.382(2) Å, β = 90.00(2)°, Z = 4, and V = 3162(1) Å3. © 1997 Elsevier Science S.A.