Organometallic oxides and sulfides: preparation of [(η-C5H5)Ti]5(μ3-S)6, [(η-C5H5)Ti]5(μ3-S)5(μ3-S2)(μ4-O), and(η-C5H5)2Ti(SH)(μ-O)Ti(η-C5H5)(μ-S)2- Ti(η-C5H5)2 by reductive aggregation of (η-C5H5)2Ti(SH)2 with zinc powder or by oxidation of (η-C5H5)2Ti(CO)2 with H2S in the presence of water

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Abstract
Reduction of (η-C5H5)2Ti(SH)2 with zinc powder gave a mixture of products, of which [(η-C5H5)Ti]5(μ3-S)6 (1), [(η-C5H5)Ti]5(μ3-S)5(μ3-S2)(μ4-O)(2),(η-C5H5)2Ti(SH)(μ-O)Ti(η-C5H5)(μ-S)2Ti(η-C5H5)2 (3),[(η-C5H5)Ti]4(μ2-S2)4(μ2-O)(μ4-O) (4), and [(η-C5H5)Ti(μ3-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 (η-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 Å, average Ti(eq)—Ti(eq) distance 3.24 Å) except for one long equatorial Ti—Ti edge of 3.60 Å, which is spanned by the μ3-S2 unit. 2 is monoclinic, P21/n, a = 10.585(1), b = 28.133(4), c = 31.408(2) Å, β = 91.20(1)°, 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, a = 9.146(1), b = 12.290(1), c = 13.027(1) Å, α = 100.72(1), β = 104.39(1), γ = 110.55(1)°, Z = 2, R = 0.037 for 3046 observed reflections and 304 parameters. The Ti—O—Ti unit in 3 has an angle of 175.6(2)°.
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