• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

烃溶性碱金属铝氢化物替代物

Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES].

作者信息

Banerjee Sumanta, Macdonald Peter A, Orr Samantha A, Kennedy Alan R, van Teijlingen Alexander, Robertson Stuart D, Tuttle Tell, Mulvey Robert E

机构信息

WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.

出版信息

Chemistry. 2022 Oct 4;28(55):e202201085. doi: 10.1002/chem.202201085. Epub 2022 Aug 11.

DOI:10.1002/chem.202201085
PMID:35811447
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9804340/
Abstract

A series of group 1 hydrocarbon-soluble donor free aluminates [AM( BuDHP)(TMP)Al( Bu) ] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- BuC H N)AM)] containing a surrogate hydride (sp C-H) with [( Bu) Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li( BuDHP)(TMP)Al( Bu) ] and [(TMEDA)Na( BuDHP)(TMP)Al( Bu) ] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].

摘要

通过将含有替代氢化物（sp³ C-H）的碱金属二氢吡啶基单元[(2-BuC₅H₄N)AM)]与[(Bu)₂Al(TMP)]相结合，合成了一系列第1组烃溶性无供体铝酸盐[AM(BuDHP)(TMP)Al(Bu)]（AM = Li、Na、K、Rb）。这些铝酸盐已通过X射线晶体学和核磁共振光谱进行了表征。虽然锂铝酸盐形成单体，但较重的碱金属铝酸盐以聚合物链的形式存在，这些聚合物链通过碱金属阳离子与烷基二氢吡啶基单元之间的非共价相互作用而扩展。溶剂化物[(THF)Li(BuDHP)(TMP)Al(Bu)]和[(TMEDA)Na(BuDHP)(TMP)Al(Bu)]也已通过晶体学进行了表征。理论计算表明，与稳定化静电力相比，从Li到Rb时色散力倾向于增加，而稳定化静电力的量级要大得多。这些双金属化合物具有独特的结构特征，可被视为探索作为碱金属 - 铝氢化物替代物的独特反应趋势的起点。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/834a0e239850/CHEM-28-0-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/77b5674d4171/CHEM-28-0-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/d9283fce3e7d/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/63a983bd04e6/CHEM-28-0-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/16c474e21cbf/CHEM-28-0-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/97463e2287e5/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/35f6fbfe13fe/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/7819f0f94d6e/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/9e6c878c5fba/CHEM-28-0-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/188ba5f4c184/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/daec4f33b8f7/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/834a0e239850/CHEM-28-0-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/77b5674d4171/CHEM-28-0-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/d9283fce3e7d/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/63a983bd04e6/CHEM-28-0-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/16c474e21cbf/CHEM-28-0-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/97463e2287e5/CHEM-28-0-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/35f6fbfe13fe/CHEM-28-0-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/7819f0f94d6e/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/9e6c878c5fba/CHEM-28-0-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/188ba5f4c184/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/daec4f33b8f7/CHEM-28-0-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6021/9804340/834a0e239850/CHEM-28-0-g010.jpg

相似文献

1
Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES].烃溶性碱金属铝氢化物替代物
Chemistry. 2022 Oct 4;28(55):e202201085. doi: 10.1002/chem.202201085. Epub 2022 Aug 11.
2
Developing a hetero-alkali-metal chemistry of 2,2,6,6-tetramethylpiperidide (TMP): stoichiometric and structural diversity within a series of lithium/sodium, lithium/potassium and sodium/potassium TMP compounds.发展 2,2,6,6-四甲基哌啶（TMP）的杂碱金属化学：一系列锂/钠、锂/钾和钠/钾 TMP 化合物中的化学计量和结构多样性。
Chemistry. 2011 Aug 1;17(32):8820-31. doi: 10.1002/chem.201101167. Epub 2011 Jul 15.
3
Synthesis, Characterization, and Structural Analysis of [Al(NON)(H)(SiHPh)] ( = Li, Na, K, Rb, Cs) Compounds, Made Via Oxidative Addition of Phenylsilane to Alkali Metal Aluminyls.[Al(NON)(H)(SiHPh)]（=Li、Na、K、Rb、Cs）化合物的合成、表征和结构分析，通过苯硅烷对碱金属铝烷的氧化加成制备得到。
Inorg Chem. 2022 Dec 12;61(49):19838-19846. doi: 10.1021/acs.inorgchem.2c03010. Epub 2022 Nov 23.
4
New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide.叔芳酰胺定向邻位铝化反应中碱金属介导的铝化反应的新反应活性及结构见解
Chem Commun (Camb). 2006 Aug 14(30):3208-10. doi: 10.1039/b606080c. Epub 2006 Jun 19.
5
Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent-Induced Dissociation Effects.重碱金属锰酸盐配合物：合成、结构及溶剂诱导解离效应
Chemistry. 2022 Oct 4;28(55):e202201716. doi: 10.1002/chem.202201716. Epub 2022 Aug 3.
6
Influence of alkali metal cations on the formation of the heterobimetallic actinide -butoxides [AnM(OBu)] and [AnM(OBu)] (An = Th, U; M = Li, Na, K, Rb, Cs).碱金属阳离子对异双金属锕系元素 - 丁氧基化物 [AnM(OBu)] 和 [AnM(OBu)] 的形成的影响（An = Th, U；M = Li, Na, K, Rb, Cs）。
Dalton Trans. 2023 Jan 24;52(4):962-970. doi: 10.1039/d2dt01316a.
7
Meta-metallation of N,N-dimethylaniline: Contrasting direct sodium-mediated zincation with indirect sodiation-dialkylzinc co-complexation.N,N-二甲基苯胺的间位金属化：直接的钠介导锌化与间接的钠-二烷基锌共络合的对比。
Beilstein J Org Chem. 2011;7:1234-48. doi: 10.3762/bjoc.7.144. Epub 2011 Sep 6.
8
Heterobimetallic metallation studies of N,N-dimethylphenylethylamine (DMPEA): benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex.N,N-二甲基苯乙胺（DMPEA）的异双金属金属化研究：苄基C-H键裂解/二甲氨基捕获或完整的DMPEA配合物。
Dalton Trans. 2015 Mar 28;44(12):5875-87. doi: 10.1039/c5dt00247h.
9
Synthesis, structures, and conformational characteristics of calixarene monoanions and dianions.杯芳烃单阴离子和双阴离子的合成、结构及构象特征
J Am Chem Soc. 2003 May 21;125(20):6228-38. doi: 10.1021/ja0289797.
10
Structural variations within group 1 (Li-Cs)+ (2,2,6,6-tetramethyl-1-piperidinyloxy)- complexes made via metallic reduction of the nitroxyl radical.通过硝氧自由基的金属还原反应合成的第 1 组（Li-Cs）+（2,2,6,6-四甲基-1-哌啶氧基）-配合物的结构变化。
Inorg Chem. 2009 Jul 20;48(14):6934-44. doi: 10.1021/ic900609e.

引用本文的文献

1
Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine.一种由取代的4-(二甲基氨基)吡啶活化的氢化钠可溶性分子载体的合成、表征及催化应用
Commun Chem. 2024 Apr 27;7(1):94. doi: 10.1038/s42004-024-01184-5.
2
Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy.碱金属二氢吡啶在亚胺转移氢化催化中的作用：酰胺碱性与氢化物替身。
Angew Chem Int Ed Engl. 2023 Jul 3;62(27):e202304966. doi: 10.1002/anie.202304966. Epub 2023 May 22.

本文引用的文献

1
Inhibition of Alkali Metal Reduction of 1-Adamantanol by London Dispersion Effects.伦敦色散效应抑制1-金刚烷醇的碱金属还原反应
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202201318. doi: 10.1002/anie.202201318. Epub 2022 Mar 30.
2
Rubidium and caesium aluminyls: synthesis, structures and reactivity in C-H bond activation of benzene.铷和铯铝化物：苯C-H键活化中的合成、结构及反应活性
Chem Commun (Camb). 2022 Jan 27;58(9):1390-1393. doi: 10.1039/d1cc05379e.
3
Contrasting the Mechanism of H Activation by Monomeric and Potassium-Stabilized Dimeric Al Complexes: Do Potassium Atoms Exert any Cooperative Effect?
单体和钾稳定二聚体铝配合物激活氢的机制对比：钾原子是否发挥协同效应？
Chemistry. 2021 Dec 9;27(69):17369-17378. doi: 10.1002/chem.202103082. Epub 2021 Oct 22.
4
Molecular Main Group Metal Hydrides.分子主族金属氢化物
Chem Rev. 2021 Oct 27;121(20):12784-12965. doi: 10.1021/acs.chemrev.1c00278. Epub 2021 Aug 27.
5
Factors Controlling the Aluminum(I)-meta-Selective C-H Activation in Arenes.芳烃中控制铝（I）间位选择性C-H活化的因素。
Chemistry. 2021 Aug 25;27(48):12422-12429. doi: 10.1002/chem.202101944. Epub 2021 Jul 22.
6
Main group bimetallic partnerships for cooperative catalysis.用于协同催化的主要主族双金属组合
Chem Sci. 2020 Oct 16;12(6):1982-1992. doi: 10.1039/d0sc05116k.
7
Facilitating the Ferration of Aromatic Substrates through Intramolecular Sodium Mediation.通过分子内钠介导促进芳基底物的铁化。
Angew Chem Int Ed Engl. 2021 Jul 5;60(28):15296-15301. doi: 10.1002/anie.202104275. Epub 2021 Jun 17.
8
Strongly reducing magnesium(0) complexes.强烈还原镁(0)配合物。
Nature. 2021 Apr;592(7856):717-721. doi: 10.1038/s41586-021-03401-w. Epub 2021 Apr 28.
9
Selective Cross-Coupling of Unsaturated Substrates on Al.铝上不饱和底物的选择性交叉偶联
Chemistry. 2021 Mar 26;27(18):5730-5736. doi: 10.1002/chem.202004907. Epub 2021 Mar 1.
10
Alkali-Metal Mediation: Diversity of Applications in Main-Group Organometallic Chemistry.碱金属介导：在主族有机金属化学中的应用多样性
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9247-9262. doi: 10.1002/anie.202010963. Epub 2020 Dec 3.