Half-sandwich titanium complexes with β-oxodithioester ligands

The reaction of CpTiCl3 with HLx [HLx = methyl 3-(4'-X-phenyl)-3-hydroxy-2-propenedithioate ligands; X = H(1), Me(2), OMe(3), Cl(4), Br(5)] in the presence of NEt3 yielded the corresponding half-sandwich complexes TiCpCl2(L-x) [X = H(6), Me(7), OMe(8), Cl(9), Br(10)]. Compounds 1-10 were characterized by elemental analyses, infrared, H-1 and C-13 NMR spectroscopy and EI mass spectrometry, while ligands 1,3-5 and complexes 6-10 were also characterized by single-crystal X-ray diffraction studies. The structural arrangements observed in 1,3-5 include an intramolecular O-H center dot center dot center dot S hydrogen bond. The metal center in 6-10 exhibits a square pyramidal geometry by means of the O boolean AND S coordination mode of ligands, which led to the racemic form of the A, C enantiomers, associated by an inversion center. (C) 2014 Elsevier B. V. All rights reserved.