Monocyclopentadienyl titanium complexes supported by functionalized Shiff Base ligands

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• 作者：Rosa Fandos^a ; ; Antonio Otero^b ; ^{antonio.otero@uclm.es" class="auth_mail} ; Ana M. Rodrí ; guez^c ; Sara Suizo^a
• 关键词：Carboxylate ; Aminocarbene ; Tridentate ligands ; Titanium complexes
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 June, 2014
• 年：2014
• 卷：759
• 期：Complete
• 页码：74-82
• 全文大小：1235 K

文摘

The titanium derivatives [TiCp聽*聽Me(魏³-ONO-OOCPhNCHPhO)] (1), [TiCp聽*聽Me(魏³-ONO-OCH₂PhNCHPhO)] (2) and [TiCp聽*聽Me(魏³-ONS-SPhNCHPhO)] (3) have been synthesized by reaction of [TiCp聽*聽Me₃] (Cp*聽=聽畏⁵-C₅Me₅) with 2-(salicylideneamino)benzoic acid, 2-(hydroxybenzyl)salicylideneamino or 2-(salicylideneamino)thiophenol, respectively, in a聽1:1聽M ratio. The reaction of [TiCp聽*聽Me₃] with and 2-(salicylideneamino)thiophenol in 1:2聽M ratio yields the titanium compound [TiCp聽*聽Me(魏³-ONS-SPhNCHPhO)(魏¹-O-PhCHNHPhS)] (5) Complexes 1, 2 and 3 react with ^tBuNC to yield the iminoacyl-containing compounds [TiCp聽*聽(畏²-CN-MeCN^tBu)(魏³-ONO-OOCPhNCHPhO)] (6), [TiCp聽*聽(畏²-CN-MeCN^tBu)(魏³-ONO-OCH₂PhNCHPhO)] (7) and [TiCp聽*聽(畏²-CN-MeCN^tBu)(魏³-ONS-SPhNCHPhO)] (8). Compounds 7 and 8 can be protonated with triflic acid to yield the aminocarbene derivatives (9) and (10), respectively. Moreover, the reaction of complexes 1-3 with triflic acid renders the corresponding triflate compounds [TiCp聽*聽(魏³-ONO-OOCPhNCHPhO)(OTf)] (11), [TiCp聽*聽(魏³-ONO-OCH₂PhNCHPhO)(OTf)] (12) and [TiCp聽*聽(魏³-ONS-SPhNCHPhO)(OTf)] (13). The reaction of 1 or 2 with B(C₆F₅)₃ in a 1:1聽M ratio yields the carboxylate adduct [TiCp聽*聽Me(魏³-ONO-OOCPhNCHPhO路B(C₆F₅)₃)] (14) or the cationic derivative. [TiCp聽*聽(魏³-ONO-OCH₂PhNCHPhO)]₂[MeB(C₆F₅)₃)]₂ (15), respectively. The molecular structures of complexes 2, 5, 6, 13 and 15 have been established by X-ray diffraction methods.