Sodium Aminodiboranates Na(H 3 BNR 2 BH 3 ): Structural and Spectroscopic Studies of Steric and Electronic Substituent Effects
Sodium Aminodiboranates Na(H 3 BNR 2 BH 3 ): Structural and Spectroscopic Studies of Steric and Electronic Substituent Effects
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氨基二硼酸钠 Na(H 3 BNR 2 BH 3 )：空间和电子取代基效应的结构和光谱研究
DOI：
10.1021/acs.inorgchem.2c01997
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发表时间：
2022
影响因子：
4.6
通讯作者：
Girolami, Gregory S.
中科院分区：
文献类型：
--
作者：
Caroff, Christopher M.;Bellott, Brian J.;Daly, Connor I.;Daly, Scott R.;Dunbar, Andrew C.;Mallek, Justin L.;Nesbit, Mark A.;Girolami, Gregory S.
本文叙述了一系列氨基二硼酸钠盐的合成，（H3 B-NR 2-BH 3），在氮上具有不同取代基，包括未取代的氨基二硼杂环丁烷、H3 B-NH 2-BH 3-和N-取代的阴离子H3 B-NRR ′-BH 3-的钠盐，其中NRR′ = NHMe、NHEt、NH（SiMe 3）、NEt 2、N（i-Pr）2、N（SiMe 3）2、NMe（i-Pr）、NMe（t-Bu）、NMe（SiMe 3），以及吡咯烷和哌啶衍生物NC 4 H8、NC 5 H10和NC 5 H8-顺式-2，6-Me 2。这些化合物已经通过1H和11B NMR光谱和IR光谱进行了表征;对未溶剂化的N，N-二甲基氨基二硼氢化钠盐Na（H3 B-NMe 2-BH 3）和几种氨基二硼氢化钠盐进行了晶体学研究，其中钠离子与醚（二氧六环、二甘醇二甲醚、四氢呋喃和12-冠-4）或胺（N，N，N′，N′-四甲基乙二胺）溶剂化。其中一种结构包含一种罕见的醚配体，其中一个氧原子桥接两个金属离子。一般的结构和光谱的趋势作为氮上的取代基的函数进行了讨论。
We describe the syntheses of a series of sodium aminodiboranate salts, Na(H3B–NR2–BH3), with different substituents on nitrogen, including sodium salts of the unsubstituted aminodiboranate, H3B−NH2−BH3–, and of the N-substituted anions H3B−NRR′−BH3–, where NRR′ = NHMe, NHEt, NH(SiMe3), NEt2, N(i-Pr)2, N(SiMe3)2, NMe(i-Pr), NMe(t-Bu), NMe(SiMe3), and the pyrrolidide and piperidide derivatives NC4H8, NC5H10, and NC5H8-cis-2,6-Me2. The compounds have been characterized by1H and11B NMR spectroscopy and IR spectroscopy; crystallographic studies have been carried out for the unsolvatedN,N-dimethylaminodiboranate salt Na(H3B−NMe2−BH3) and several sodium aminodiboranate salts in which the sodium ions are solvated with ethers (dioxane, diglyme, tetrahydrofuran, and 12-crown-4) or amines (N,N,N′,N′-tetramethylethylenediamine). One of the structures contains a rare example of an ether ligand in which one oxygen atom bridges between two metal ions. General structural and spectroscopic trends as a function of the substituents on nitrogen are discussed.