Migratory Insertion and Reductive Coupling of Tetraarylruthenium(IV) Complexes

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• 作者：Shiu-Chun So ; Wai-Man Cheung ; Guo-Cang Wang ; Enrique Kwan Huang ; Man-Kit Lau ; Qian-Feng Zhang ; Herman H.-Y. Sung ; Ian D. Williams ; Wa-Hung Leung
• 刊名：Organometallics
• 出版年：2014
• 出版时间：September 8, 2014
• 年：2014
• 卷：33
• 期：17
• 页码：4497-4502
• 全文大小：399K
• ISSN：1520-6041

文摘

Tetraarylruthenium(IV) complexes have been synthesized and their migratory insertion, reductive coupling, and bromination reactions investigated. Treatment of [Ru(acac)₃] (acac^{鈥?/sup> = acetylacetonate) with RMgBr, followed by column chromatography in air afforded the tetraaryl complexes [RuR₄] (R = 2,5-dimethylphenyl (R1); 4-methoxy-2-methylphenyl (R2)). Oxidation of [RuR2₄] with AgBF₄ gave the Ru(V) complex [RuVR2₄](BF₄), which has a measured 渭_eff of 1.8 渭_B. [RuR₄] and can catalyze the oxidation of methyl p-tolyl sulfide with PhIO. Reaction of [RuR2₄] with PhICl₂ led to C鈥揅 reductive coupling and the formation of the Ru(II) 畏6-biaryl complex [(畏6-R2-R2)RuCl₂]₂ (1). Treatment of [RuR1₄] with excess NO gave the tetranuclear Ru(II) aryl-N-nitrosohydroxylaminato complex [RuR1(N){魏₂-O,O鈥?ON(R1)NO}(渭-NO₂)]₄ (2). Bromination of [RuR1₄] with N-bromosuccinimide resulted in formation of [RuR鈥?sub>4] (R鈥?= 4-bromo-2,5-dimethylphenyl) (3). The crystal structures of [RuR2₄], [RuR2₄](BF₄), and 1鈥?b>3 have been determined.}