This paper-is dedicated to Professor Zdenek (Denny) Valenta on the occasiotl of his 6Stl1 birthdayFRANK BOTTOMLEY and ROBERT W. DAY. Can. J. Chem. 70, 1250 (1 992). Reduction of (q-CSH5)2Ti(SH)2 with zinc powder gave a mixture of products, of which [(q-C5Hs)Ti]5(p3-s)6 (I), [(q-
CsHs)Til,(~3-S)s(~3-S~)(~~-O) (21, (T-CSH~)~T~(SH)(~L-O)T~(T-C~HS)(CL-S)~T~(T-C~S (3), [(T-CSH~)T~I~(CL?-SZ)~(P?-O)(0) (4), and [(T-C,H~)T~(CL~-S)], (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 thc zinc powder. A similar mixture of products was obtained from the reaction between (TCsH,)2Ti(C0)2 and H?S 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 A, average Ti(eq)-Ti(eq) distance 3.24 A) except for one long equatorial Ti-Ti edge of 3.60 i\, which is spanned by the p3-S2 unit. 2 is monoclinic, P 2 , / n ,
(T-CSH~)T~I~(CL~-S)~(CL~-S~)(CL,-O) (21, (T-CSH~)?T~(SH)(~-O)T~(T-C~H~)(CL-S)?T~(~-(31, [(q-C,H,)Ti],(p,-S2),(p2-O)(k,-0) (4) et [(q-C,Hs