Further Studies of Co III (TIM) Mono‐Alkynyl and Bis‐Alkynyl Complexes
Further Studies of Co III (TIM) Mono‐Alkynyl and Bis‐Alkynyl Complexes
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Co III (TIM) 单炔基和双炔基配合物的进一步研究
DOI：
10.1002/ejic.202200641
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发表时间：
2022
影响因子：
2.3
通讯作者：
Ren, Tong
中科院分区：
文献类型：
--
作者：
Rodriguez Segura, Leobardo;Cox, Kenneth E.;Samayoa‐Oviedo, Hugo Y.;Ren, Tong
本文报道了一系列新的单炔基和双炔基Co III（TIM）配合物（TIM= 2，3，9，10-四甲基-1，4，8，11-四氮杂环十四碳-1，3，8，10-四烯）。在Et 3 N存在下，由trans-[Co（TIM）Cl 2] PF 6与HC 2 R（R=三异丙基硅或TIPS（1），-C6 H4 - 4-tBu（2），-C6 H4 - 4-NO2（3 a），和N-均三甲苯基-1，8-萘酰亚胺或NAPMes（4 a））反应制备了trans-[Co（TIM）（C2 R）Cl]+配合物.用AgOTf分别与3 a和4 a在乙腈中反应，得到了反式-[Co（TIM）（C2 R）（NCMe）]（PF 6）（OTf）3带4 B的中间体配合物。此外，在Et 3 N存在下，3 band 4 B分别与适当的HC 2 R发生第二次脱卤化氢反应，生成了双炔基反式[Co（TIM）（C2 R）2] PF 6配合物3和4 c.这些新的配合物已通过X射线衍射（2，3 a，4 a，和4 c），IR，1H NMR，UV/维斯光谱，荧光光谱（4 c）和循环伏安法进行了表征。
A new series of mono‐ and bis‐alkynyl CoIII(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. Thetrans‐[Co(TIM)(C2R)Cl]+complexes were prepared from the reaction betweentrans‐[Co(TIM)Cl2]PF6and HC2R (R=tri(isopropyl)silyl or TIPS (1), ‐C6H4‐4‐tBu (2), ‐C6H4‐4‐NO2(3 a), andN‐mesityl‐1,8‐naphthalimide or NAPMes(4 a)) in the presence of Et3N. The intermediate complexes of the typetrans‐[Co(TIM)(C2R)(NCMe)](PF6)(OTf),3 band4 b, were obtained by treating3 aand4 a, respectively, with AgOTf in CH3CN. Furthermore, bis‐alkynyltrans‐[Co(TIM)(C2R)2]PF6complexes,3 cand4 c, were generated following a second dehydrohalogenation reaction between3 band4 b, respectively, and the appropriate HC2R in the presence of Et3N. These new complexes have been characterized using X‐ray diffraction (2,3 a,4 a, and4 c), IR,1H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c), and cyclic voltammetry.