AbstractConversions of organoelement diamides, ArDippE(NMe2)2 (E=Sb, Bi; ArDipp=C6H3‐2,6‐Dipp2), with Ph2SnH2 as reducing agent gave access to low‐valent, heavier group 15 dimers ArDippSb=SbArDipp and ArDippBi=BiArDipp, while only readily removable byproducts (i. e. dihydrogen, amines) and cyclo‐(Ph12Sn6) are generated during the reaction. Moreover, experiments involving the reaction of organoantimony hydride species Ar*2SbH (Ar*=C6H2‐2,6‐(Ph2CH)2‐4‐iPr) with Bi(NEt2)3 yielded a second novel distibene, Ar*Sb=SbAr*, with the currently longest Sb−Sb bond distance of 2.8605(5) Å in a distibene. In conversions of TbbSnH3 (Tbb=C6H2‐2,6‐(CH(SiMe3)2)2‐4‐tBu) with Bi(NEt2)3, ligand migration resulted in the isolation of TbbBi=BiTbb. Remarkably, the herein reported novel inorganic coupling route enables preparation and isolation of heavier dipnictenes without the formation of inorganic salts. All four low‐oxidation state compounds were isolated and subsequently characterized using state of the art techniques, i. e. X‐ray crystallography, NMR and UV/Vis spectroscopy.
摘要有机元素二酰胺 ArDippE(NMe2)2 (E=Sb、Bi;ArDipp=C6H3-2,6-Dipp2)与 Ph2SnH2 作为还原剂进行转化,可获得低价、较重的第 15 族二酰胺 ArDippSb=SbArDipp 和 ArDippBi=BiArDipp,而反应过程中仅生成易去除的副产物(即二氢、胺)和环(Ph12Sn6)。此外,在有机锑氢化物 Ar*2SbH(Ar*=C6H2-2,6-(Ph2CH)2-4-iPr)与 Bi(NEt2)3 反应的实验中,产生了第二种新型二孪烯 Ar*Sb=SbAr*,其 Sb-Sb 键距离为目前二孪烯中最长的 2.8605(5)埃。在 TbbSnH3(Tbb=C6H2-2,6-(CH(SiMe3)2)2-4-tBu)与 Bi(NEt2)3 的转化过程中,配体迁移导致分离出 TbbBi=BiTbb。值得注意的是,本文所报道的新型无机偶联路线能够在不形成无机盐的情况下制备和分离出更重的二壬烯。所有四种低氧化态化合物都已分离出来,并随后利用最先进的技术(即 X 射线晶体学、核磁共振)对其进行了表征。X 射线晶体学、核磁共振和紫外/可见光谱。