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

Abstract

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

Titanium(IV) Neopentoxides. X-ray Structures of Ti3(μ3-O)(μ3-Cl)(μ-OCH2CMe3)3(OCH2CMe3)6and [Ti(μ-OCH2CMe3)(OCH2CMe3)3]2

“…This is due to the symmetrical constraints induced by the two capping ligands. The average Ti−ONp, Ti−(μ-ONp), and Ti---Ti distances of 1.78, 2.03, and 3.04 Å, respectively, fall within the ranges reported for other Ti alkoxides. − ,− The Ti−(μ 3 -Cl) distances of 1 (average 2.78 Å) is the longest observed, 2.470(5)−2.684(2) Å, − whereas the Ti−(μ 3 -O) distance of 1.93 Å (average) is one of the shortest distances reported for μ 3 -oxo ligands, 1.962(4)−2.088(8) Å. − ,− The angles adopted around the various metal centers of 1 are consistent with a slightly distorted octahedral geometry. The Ti−(μ 3 -OR)−Ti angle of 103.6° is consistent with other μ 3 -O ligated compounds. ,, The Ti−(μ-OR)−Ti angles of 96.6° (average) and the Ti−(μ 3 -Cl)−Ti angles of 66.2° (average) are the smallest angles reported for titanium alkoxides which range from 104 to 112° and 73.7(1) to 114.3(1)°, respectively. ,,, …”

Organometallic Oxides: Preparation and Properties of the Clusters [(η-C5Me5)V(μ3-O)]4and [(η-C5Me5)V]4(μ-O)6by Reductive Aggregation of (η-C5Me5)VCl2(O)

“…In addition to the adamantane structure 2 , two other structures are known or have been proposed for [Cp‘M] 4 A 6 clusters. − Structure 10 was found for [Cp*Ti] 4 (μ 2 −Se) 3 (μ 3 −Se) 3 . Structure 11 was proposed for the cluster [Cp*Nb] 4 O 6 from spectroscopic evidence, and Bénard and co-workers calculated by ab initio methods that structure 11 , with D 2 h symmetry, was 26 kcal mol -1 more stable than the adamantane structure 2 for [Cp*V] 4 (μ-O) 6 .…”

Formation of an Anionic Titanium(IV) Sulfido Dimer, {Na2[CpTi(μ-S)(S)]2·4THF}2, by Elimination of CpH and H2from Cp2Ti(SH)2upon Deprotonation with NaH

“…One of the older examples, Cp 2 Ti(SH) 2 , was first synthesized by Köpf and Schmidt in 1965 . The preparation was improved in 1980 by McCall and Shaver, but the reactivity of Cp 2 Ti(SH) 2 in the literature is limited . Important questions are whether deprotonated anionic forms of hydrosulfide complexes are stable and whether they show higher reactivity than neutral sulfides with electrophiles such as SO 2 .…”