A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities
A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities
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意外登陆大环二桥头二有机胂的未知领域：合成、结构和反应性
DOI：
10.1039/d2cc03235j
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发表时间：
2022
影响因子：
4.9
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
--
作者：
Zarcone, Samuel R.;Verardi, Peter J.;Bhuvanesh, Nattamai;Gladysz, John A.
trans-[Fe(CO)2(NO)(As((CH2)n)3As)]+ BF4− (n = 10, 12, 14) 和 Bu4N+ Cl− 的反应得到标题化合物 As((CH2)n)3As，其与 MCl2 (M = Pt, Ni)、Rh(CO)(Cl) 和 Fe(CO)3 源反应 (n = 14) 重新构成笼状配合物反式-MLn(As((CH2)14)3As)。与H2O2和BH3反应生成相应的砷化氢氧化物和硼烷。无金属物质的晶体结构揭示了异构体，但笼络合物的形成被认为需要同构异构化为具有内定向孤对的异构体。
Reactions of trans-[Fe(CO)2(NO)(As((CH2)n)3As)]+ BF4− (n = 10, 12, 14) and Bu4N+ Cl− afford the title compounds As((CH2)n)3As, which upon reaction (n = 14) with MCl2 (M = Pt, Ni), Rh(CO)(Cl), and Fe(CO)3 sources reconstitute cage like complexes trans-MLn(As((CH2)14)3As). Reactions with H2O2 and BH3 give the corresponding arsine oxides and boranes. Crystal structures of metal-free species reveal out,out isomers, but cage complex formation is proposed to entail homeomorphic isomerization to in,in isomers with endo directed lone pairs.