ORGANOMETALLIC OXIDES AND SULFIDES - PREPARATION OF [(ETA-C5H5)TI]5(MU-3-S)6, [(ETA-C5H5)TI]5(MU-3-S)5(MU-3-S2)(MU-4-O), AND (ETA-C5H5)2TI(SH)(MU-O)TI(ETA-C5H5)(MU-S)2-TI(ETA-C5H5)2 BY REDUCTIVE AGGREGATION OF (ETA-C5H5)2TI(SH)2 WITH ZINC POWDER OR BY OXIDATION OF (ETA-C5H5)2TI(CO)2 WITH H2S IN THE PRESENCE OF WATER

Reduction of (eta-C5H5)2Ti(SH)2 with zinc powder gave a mixture of products, of which [(eta-C5H5)Ti]5(mu-3-S)6 (1), [(eta-C5H5)Ti]5(mu-3-S)5(mu-3-S2)(mu-4-O) (2), (eta-C5H5)2Ti(SH)(mu-O)Ti(eta-C5H5)(mu-S)2Ti(eta-C5H5)2 (3), [(eta-C5H5)Ti]4(mu-2-S2)4(mu-2-O)(mu-4-O) (4), and [(eta-C5H5)Ti(mu-3-S)]4 (5) were identified by a combination of fractional crystallization and X-ray diffraction, electron spin resonance spectroscopy, or mass spectrometry. The source of the oxygen in 2, 3, and 4 is believed to be the zinc oxide coating on the zinc powder. A similar mixture of products was obtained from the reaction between (eta-C5H5)2Ti(CO)2 and H2S in the presence of small quantities of water. The structures of 2 and 3 are discussed in detail. 2 has a trigonal bipyramidal arrangement of Ti atoms (average Ti(ax)-Ti(eq) 3.22 angstrom, average Ti(eq)-Ti(eq) distance 3.24 angstrom) except for one long equatorial Ti-Ti edge of 3.60 angstrom, which is spanned by the mu-3-S2 unit. 2 is monoclinic, P2(1)/n, a = 10.585(1), b = 28.133(4), c = 31.408(2) angstrom, beta = 91.20(1)-degrees, Z = 4 (for three independent molecules of 2 and one C6H5CH3), R = 0.071 for 6911 observed reflections and 1141 refined parameters. 3 is triclinic, P1BAR, a = 9.146(1), b = 12.290(1), c = 13.027(1) angstrom, alpha = 100.72(1), beta = 104.39(1), gamma = 110.55(1)-degrees, Z = 2, R = 0.037 for 3046 observed reflections and 304 parameters. The Ti-O-Ti unit in 3 has an angle of 175.0(2)-degrees.