Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku Kyoto, 606-8502, Japan.
Chemistry. 2019 Jan 7;25(2):521-525. doi: 10.1002/chem.201805491. Epub 2018 Dec 13.
An azepine-fused Ni -porphyrin dimer was synthesized by oxidative amination of β-β linked Ni -porphyrin dimer, and its N-aryl congener was synthesized by twofold Buchwald-Hartwig amination of β-to-β linked and dichlorinated Ni -porphyrin dimer. Oxidation of the NH congener gave neutral aminyl radical and nitrenium ion successively in a similar manner to the previously reported NH-bridged Ni -porphyrin dimer. Oxidation of the N-aryl congener afforded formal nitrenium dication in a single-step two-electron oxidation. Stable nitrenium dications that are isoelectronic to neutral trivalent boron compounds and tertiary carbocations are rare. The chemical stability of the nitrenium dication was improved by chlorine substitution at the most reactive β-position. The structural, optical, magnetic, electrochemical properties of these compounds were fully characterized.
通过β-β 连接的镍卟啉二聚体的氧化氨化合成了一个氮杂菲并合的镍卟啉二聚体，通过β-到-β 连接和二氯化镍卟啉二聚体的双重 Buchwald-Hartwig 氨化合成了其 N-芳基同系物。NH 同系物的氧化以类似于先前报道的 NH 桥连的镍卟啉二聚体的方式，依次产生中性氨自由基和氮宾离子。N-芳基同系物的氧化在一步双电子氧化中得到了形式上的氮宾二阳离子。与中性三价硼化合物和叔碳阳离子等电子的稳定氮宾二阳离子很少见。通过在最活泼的β-位取代氯，改善了氮宾二阳离子的化学稳定性。这些化合物的结构、光学、磁性和电化学性质都得到了充分的表征。
