Hydropnictination Reactions of Carbodiimides and Isocyanates with Protonated Heptaphosphide and Heptaarsenide Zintl Ions
Hydropnictination Reactions of Carbodiimides and Isocyanates with Protonated Heptaphosphide and Heptaarsenide Zintl Ions
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碳二亚胺和异氰酸酯与质子化七磷化物和七砷化物 Zintl 离子的氢化反应
DOI：
10.1002/ejic.201301011
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发表时间：
2014
影响因子：
2.3
通讯作者：
J. Goicoechea
中科院分区：
文献类型：
--
作者：
Robert S. P. Turbervill;J. Goicoechea
采用与合成[HP 7]2-（1）类似的方法，合成了七砷化氢二价阴离子[HAs 7]2-（2）。基于先前的研究，已经表明[HP 7]2-可以与双酰亚胺反应产生脒官能化簇阴离子[P7 C（NHR）（NR）]2-，我们发现类似的氢化反应也可以通过2与RC=N=CR反应产生[As 7 C（NHR）（NR）]2- [R = Dipp（3），iPr（4）和Cy（5; Dipp = 2，6-二异丙基苯基]。此外，我们还证明了这样的氢卟啉化反应可以扩展到其他杂联烯，如异氰酸酯（O=C=NAd; Ad =金刚烷基），以提供酰胺衍生的簇阴离子[E7 C（CO）（NHAd）]2- [E = P（6）和As（7）]。所有新化合物均经多核核磁共振谱、元素分析和电喷雾质谱表征。簇合物2、4、6和7还通过[K（18-冠-6）]2[2]、[K（18-冠-6）]2[4]、[K（18-冠-6）]2[6]·py（py =吡啶）和[K（18-冠-6）]2[7]·py的单晶X射线衍射进行了表征。还获得了确认阴离子3和5的组成和连接性的晶体结构。
By following a similar procedure to that employed for the synthesis of [HP7]2– (1), the synthesis and characterization of the hydrogenheptaarsenide dianion [HAs7]2– (2) was achieved. Building on previous research that has shown that [HP7]2– can react with carbodiimides to yield amidine-functionalized cluster anions [P7C(NHR)(NR)]2–, we have found that the analogous hydroarsination reactions are also possible by reaction of 2 with RC=N=CR to yield [As7C(NHR)(NR)]2– [R = Dipp (3), iPr (4) and Cy (5); Dipp = 2,6-diisopropylphenyl]. Furthermore, we also demonstrate that such hydropnictination reactions can be extended to other heteroallenes such as isocyanates (O=C=NAd; Ad = adamantyl) to afford the amide-derivatized cluster anions [E7C(CO)(NHAd)]2– [E = P (6) and As (7)]. All new compounds were characterized by multinuclear NMR spectroscopy, elemental analyses and electrospray mass spectrometry. Clusters 2, 4, 6 and 7 were also characterized by single-crystal X-ray diffraction of [K(18-crown-6)]2[2], [K(18-crown-6)]2[4], [K(18-crown-6)]2[6]·py (py = pyridine) and [K(18-crown-6)]2[7]·py. Crystal structures confirming composition and connectivity were also obtained for anions 3 and 5.