Halide, Amide, Cationic, Manganese Carbonylate, and Oxide Derivatives of Triamidosilylamine Uranium Complexes

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• 作者：Benedict M. Gardner ; William Lewis ; Alexander J. Blake ; Stephen T. Liddle
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：October 3, 2011
• 年：2011
• 卷：50
• 期：19
• 页码：9631-9641
• 全文大小：1095K
• 年卷期：v.50,no.19(October 3, 2011)
• ISSN：1520-510X

文摘

Treatment of the complex [U(Tren^TMS)(Cl)(THF)] [1, Tren^TMS = N(CH₂CH₂NSiMe₃)₃] with Me₃SiI at room temperature afforded known crystalline [U(Tren^TMS)(I)(THF)] (2), which is reported as a new polymorph. Sublimation of 2 at 160 掳C and 10^鈥? mmHg afforded the solvent-free dimer complex [{U(Tren^TMS)(渭-I)}₂] (3), which crystallizes in two polymorphic forms. During routine preparations of 1, an additional complex identified as [U(Cl)₅(THF)][Li(THF)₄] (4) was isolated in very low yield due to the presence of a slight excess of [U(Cl)₄(THF)₃] in one batch. Reaction of 1 with one equivalent of lithium dicyclohexylamide or bis(trimethylsilyl)amide gave the corresponding amide complexes [U(Tren^TMS)(NR₂)] (5, R = cyclohexyl; 6, R = trimethylsilyl), which both afforded the cationic, separated ion pair complex [U(Tren^TMS)(THF)₂][BPh₄] (7) following treatment of the respective amides with Et₃NH路BPh₄. The analogous reaction of 5 with Et₃NH路BAr^f₄ [Ar^f = C₆H₃-3,5-(CF₃)₂] afforded, following addition of 1 to give a crystallizable compound, the cationic, separated ion pair complex [{U(Tren^TMS)(THF)}₂(渭-Cl)][BAr^f₄] (8). Reaction of 7 with K[Mn(CO)₅] or 5 or 6 with [HMn(CO)₅] in THF afforded [U(Tren^TMS)(THF)(渭-OC)Mn(CO)₄] (9); when these reactions were repeated in the presence of 1,2-dimethoxyethane (DME), the separated ion pair [U(Tren^TMS)(DME)][Mn(CO)₅] (10) was isolated instead. Reaction of 5 with [HMn(CO)₅] in toluene afforded [{U(Tren^TMS)(渭-OC)₂Mn(CO)₃}₂] (11). Similarly, reaction of the cyclometalated complex [U{N(CH₂CH₂NSiMe₂Bu^t)₂(CH₂CH₂NSiMeBu^tCH₂)}] with [HMn(CO)₅] gave [{U(Tren^DMSB)(渭-OC)₂Mn(CO)₃}₂] [12, Tren^DMSB = N(CH₂CH₂NSiMe₂Bu^t)₃]. Attempts to prepare the manganocene derivative [U(Tren^TMS)MnCp₂] from 7 and K[MnCp₂] were unsuccessful and resulted in formation of [{U(Tren^TMS)}₂(渭-O)] (13) and [MnCp₂]. Complexes 3鈥?b>13 have been characterized by X-ray crystallography, ¹H NMR spectroscopy, FTIR spectroscopy, Evans method magnetic moment, and CHN microanalyses.