β,β-Diborylated Subporphyrinato Boron(III) Complexes as Useful Synthetic Precursors
β,β-Diborylated Subporphyrinato Boron(III) Complexes as Useful Synthetic Precursors
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DOI：
10.1002/anie.201503530
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发表时间：
2015-08-03
影响因子：
16.6
通讯作者：
Osuka, Atsuhiro
中科院分区：
文献类型：
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作者：
Kitano, Masaaki;Okuda, Yasuhiro;Osuka, Atsuhiro
铱催化双（pinacolato）二硼对b -芳基中位游离亚卟啉硼（III）配合物（以下简称亚卟啉）的硼化反应选择性地得到了2,13-二硼化亚卟啉，这是2,13-二氮化亚卟啉和双- 1,3-丁二炔桥接亚卟啉二聚体的有前途的合成前体。2,13-二芳基化亚卟啉显示摄动吸收光谱，这取决于-芳基取代基。由此制备的双1,3-丁二炔桥接的syn和抗亚卟啉二聚体表现出不同的吸收光谱变化，具有分裂的soet样带，这是根据激子耦合来解释的。
Iridium-catalyzed borylation of B-aryl meso-free subporphyrinato boron(III) complexes (hereinafter referred to simply as subporphyrins) with bis(pinacolato)diboron gave 2,13-diborylated subporphyrins regioselectively, which served as promising synthetic precursors for 2,13-diarylated subporphyrins and doubly -to- 1,3-butadiyne-bridged subporphyrin dimers. 2,13-Diarylated subporphyrins display perturbed absorption spectra, depending upon the -aryl substituents. Doubly 1,3-butadiyne-bridged syn and anti subporphyrin dimers thus prepared exhibit differently altered absorption spectra with split Soret-like bands, which have been accounted for in terms of exciton coupling.