Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes2 unit

Ying Li Rao; Tetsuro Kusamoto; Ryota Sakamoto; Hiroshi Nishihara; Suning Wang

doi:10.1021/om500138f

Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes₂ unit

Ying Li Rao, Tetsuro Kusamoto, Ryota Sakamoto, Hiroshi Nishihara, Suning Wang

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

A dimesitylboron-functionalized benzimidazolylferrocene, B(2-ferrocenyl-N-Me-benzimidazolyl)Mes₂ (1), has been synthesized and fully characterized. The B-N 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 ^- group. The photoisomerization process of the boron unit in 1 was fully inhibited by the low lying d-d/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.

Original language	English
Pages (from-to)	1787-1793
Number of pages	7
Journal	Organometallics
Volume	33
Issue number	7
DOIs	https://doi.org/10.1021/om500138f
Publication status	Published - 2014 Apr 14
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes2 unit",

abstract = "A dimesitylboron-functionalized benzimidazolylferrocene, B(2-ferrocenyl-N-Me-benzimidazolyl)Mes2 (1), has been synthesized and fully characterized. The B-N 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 - group. The photoisomerization process of the boron unit in 1 was fully inhibited by the low lying d-d/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.",

author = "Rao, {Ying Li} and Tetsuro Kusamoto and Ryota Sakamoto and Hiroshi Nishihara and Suning Wang",

year = "2014",

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T1 - Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes2 unit

AU - Rao, Ying Li

AU - Kusamoto, Tetsuro

AU - Sakamoto, Ryota

AU - Nishihara, Hiroshi

AU - Wang, Suning

PY - 2014/4/14

Y1 - 2014/4/14

N2 - A dimesitylboron-functionalized benzimidazolylferrocene, B(2-ferrocenyl-N-Me-benzimidazolyl)Mes2 (1), has been synthesized and fully characterized. The B-N 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 - group. The photoisomerization process of the boron unit in 1 was fully inhibited by the low lying d-d/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.

AB - A dimesitylboron-functionalized benzimidazolylferrocene, B(2-ferrocenyl-N-Me-benzimidazolyl)Mes2 (1), has been synthesized and fully characterized. The B-N 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 - group. The photoisomerization process of the boron unit in 1 was fully inhibited by the low lying d-d/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.

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Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes₂ unit

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