苯并三唑中NN的轻松活化：通过与铱络合捕获Dimroth偶氮/三唑中间体

Facile NN Activation in Benzotriazole: Capturing the Dimroth Azo/Triazole Intermediate by Complexation to Iridium.

作者信息

Bohle D Scott, Chua Zhijie, Perepichka Inna

机构信息

Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, H3A 0B8 (Canada).

出版信息

Chempluschem. 2013 Oct;78(10):1304-1310. doi: 10.1002/cplu.201300245. Epub 2013 Jul 31.

DOI:10.1002/cplu.201300245

PMID:31986781

Abstract

The in situ observation of benzotriazole ring and ring-opened isomers, which result from the Dimroth equilibrium for 1-[(nonafluorobutane)sulfonyl]benzotriazole, 1, in solution by F NMR and UV/Vis spectroscopy is reported. Two benzotriazoles, compound 1 and 1,1'-sulfonylbis(benzotriazole) (3), undergo Dimroth triazole ring opening and coordination to an iridium(I) metal center to give either linear diazo [Ir (η -NNPhNSO C F )(Cl)(PPh ) ] (2) or an unusual double bent diazene [Ir (η -NNPhNSO Btz)(Cl)(PPh ) ] (4; Btz=benzotriazole) complex.

摘要

报道了通过氟核磁共振和紫外/可见光谱对1-[(九氟丁烷)磺酰基]苯并三唑（1）在溶液中因迪姆罗思平衡而产生的苯并三唑环及其开环异构体的原位观察。两种苯并三唑，即化合物1和1,1'-磺酰基双(苯并三唑)(3)，发生迪姆罗思三唑环开环并与铱(I)金属中心配位，生成线性重氮化合物[Ir(η-NNPhNSOCF)(Cl)(PPh)] (2)或不寻常的双弯曲二氮烯[Ir(η-NNPhNSOBtz)(Cl)(PPh)] (4；Btz = 苯并三唑)配合物。