Reactivity and Electronic Properties of a Ferrocene Molecule Bearing an N,C-Chelated BMes2 Unit

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• 作者：Ying-Li Rao ; Tetsuro Kusamoto ; Ryota Sakamoto ; Hiroshi Nishihara ; Suning Wang
• 刊名：Organometallics
• 出版年：2014
• 出版时间：April 14, 2014
• 年：2014
• 卷：33
• 期：7
• 页码：1787-1793
• 全文大小：379K
• 年卷期：v.33,no.7(April 14, 2014)
• ISSN：1520-6041

文摘

A dimesitylboron-functionalized benzimidazolylferrocene, B(2-ferrocenyl-N-Me-benzimidazolyl)Mes₂ (1), has been synthesized and fully characterized. The B鈥揘 bond in 1 was found to undergo a dynamic dissociation/association process in solution, leading to a dynamic exchange of the two mesityls bound to the boron atom and slow hydrolysis of 1 under ambient conditions. The hydrolyzed product 2-BMes(OH)-1-(N-methylbenzimidazol-2-yl)ferrocene (2) was isolated and characterized, in which the boron center has a trigonal-planar geometry with one of the mesityls being replaced by an OH^{鈥?/sup> group. The photoisomerization process of the boron unit in 1 was fully inhibited by the low lying d鈥揹/MLCT states of the ferrocene unit. Compound 1 can be oxidized readily by I₂, forming the ferrocenium species [1+]I₃- (3). NMR and EPR data for 3 indicated a notable spin delocalization through space from the Fe(III) center to a flanking mesityl group.}