Reactions of Hydrogen Sulfide with Singly and Doubly Tucked-in Titanocenes

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• 作者：Jir虒i&#769 ; Pinkas ; Ivana Ci虂sar虒ova虂 ; Michal Hora虂č ; ek ; Jir虒i&#769 ; Kubis虒ta ; Karel Mach
• 刊名：Organometallics
• 出版年：2011
• 出版时间：March 14, 2011
• 年：2011
• 卷：30
• 期：5
• 页码：1034-1045
• 全文大小：1184K
• 年卷期：v.30,no.5(March 14, 2011)
• ISSN：1520-6041

文摘

Hydrogen sulfide reacts with tucked-in titanocene complexes [Ti(III){畏⁵:畏¹-C₅Me₄(CH₂)}Cp*] (Cp* = 畏⁵-C₅Me₅) (2) and [Ti{畏⁴:畏³-C₅Me₃(CH₂)₂}Cp*] (3) and their precursors [Cp*₂TiMe] (2a) and [Cp*₂Ti(畏²-Me₃SiC鈮SiMe₃)] (3a), respectively, to give the corresponding titanocene hydrosulfides [Cp*₂Ti(SH)] (4) and [Cp*₂Ti(SH)₂] (1), respectively. Hydrogen sulfide also cleaves intramolecular 蟽- or 蟺-Ti鈭扖 bonds in ansa-[Ti^III(畏¹:畏⁵:畏⁵-C₅Me₄SiMe₂CHCH₂SiMe₂C₅Me₄)] (5) and ansa-[Ti^II(畏²:畏⁵:畏⁵-C₅Me₄SiMe₂CH鈺怌HSiMe₂C₅Me₄)] (6), affording hydrosulfides ansa-[(畏⁵-CH₂Me₂SiC₅Me₄)₂Ti(SH)] (7) and ansa-[(畏⁵-CH₂Me₂SiC₅Me₄)₂Ti(SH)₂] (8). The S鈭扝 bonds of hydrosulfides 4 and 7 were able to react with the Ti鈭扖 bonds in 2 and 5, affording titanocene sulfides [(Cp*₂Ti^III)₂S] (11) and ansa-[{(畏⁵-CH₂Me₂SiC₅Me₄)₂Ti^III}₂S] (12), respectively. Combination of 7 with 2a gave rise to the mixed titanocene sulfide [ansa-{(畏⁵-CH₂SiMe₂C₅Me₄)₂Ti}S(TiCp*₂)] (13). The titanium(III) d¹ electrons in 11鈭?b>13 form an electronic triplet state well observable by EPR spectra in toluene glass. All the hydrosulfides were decomposed by sunlight. Compound 1 eliminated Cp*H and H₂S, while 4 mainly Cp*H. Apparently formed transient [Cp*TiS] species probably gave rise to the serendipitously isolated cluster [{Cp*Ti(S)}₄] (14). Crystal structures of the all complexes were determined by X-ray diffraction analysis.