Syntheses and structures of dimesitylphosphinite complexes of alkali metals and their catalytic activity in hydrophosphorylation reactions†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Benjamin E. Fener, Philipp Schüler, Phil Liebing, Helmar Görls and Matthias Westerhausen
{"title":"Syntheses and structures of dimesitylphosphinite complexes of alkali metals and their catalytic activity in hydrophosphorylation reactions†","authors":"Benjamin E. Fener, Philipp Schüler, Phil Liebing, Helmar Görls and Matthias Westerhausen","doi":"10.1039/D4DT02721C","DOIUrl":null,"url":null,"abstract":"<p >Metalation of dimesitylphosphane oxide, Mes<small><sub>2</sub></small>P(O)H (<strong>1</strong>), with alkali metal reagents (<em>n</em>BuLi, NaH, and A(hmds); A = K, Rb, and Cs) in THF yields the corresponding dimesitylphosphinites of lithium (<strong>2-thf</strong>), sodium (<strong>3-thf</strong>), potassium (<strong>4-thf</strong>), rubidium (<strong>5-thf</strong>), and caesium (<strong>6</strong>). Their molecular structures exhibit a broad and fascinating variety. Dinuclear compounds <strong>2-thf</strong>, <strong>3-thf</strong>, and <strong>5-thf</strong> have central four-membered A<small><sub>2</sub></small>O<small><sub>2</sub></small> rings, whereas the potassium congener crystallises as a tetranuclear complex with an inner A<small><sub>4</sub></small>O<small><sub>4</sub></small> heterocubane cage. The tetranuclear caesium congener precipitates without thf coligands and exhibits a quite unique structure in its crystalline state. Due to their catalytic activity in hydrophosphorylation reactions, we focus on the solvent–structure relationship of the potassium derivatives. In hydrocarbons, [K<small><sub>4</sub></small>(O-PMes<small><sub>2</sub></small>)<small><sub>4</sub></small>]<small><sub>2</sub></small> (<strong>4</strong>) is formed, and bidentate Lewis bases like dme and tmeda are unable to deaggregate this tetranuclear cage compound, but bases with a higher denticity (diglyme, triglyme, and pmdeta) split this cage compound into dinuclear complexes with central K<small><sub>2</sub></small>O<small><sub>2</sub></small> rings. In addition, very bulky <em>P</em>-bound aryl groups like 2,4,6-triisopropylphenyl in dinuclear <strong>8-thf</strong> hinder the formation of tetranuclear cage compounds, whereas 2-methylnaphthyl substituents are not bulky enough and the tetranuclear cage compound <strong>7-thf</strong> is stabilised. For the 2,4,6-triisopropylphenyl substituent, the rubidium and caesium congeners <strong>11</strong> and <strong>12</strong> crystallise with two central A<small><sub>2</sub></small>O<small><sub>2</sub></small> rings interconnected by π-interactions. A heteroleptic potassium complex <strong>9-hmds</strong>, containing hmds as well as phosphinite anions, represents a snapshot on the way from the starting K(hmds) to the phosphinite-based heterocubane congener. Finally, heterobimetallic [{(thf)K}<small><sub>2</sub></small>Mg(O-PMes<small><sub>2</sub></small>)<small><sub>4</sub></small>] (<strong>10-thf</strong>) with tetrahedrally coordinated Mg centres has been isolated.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 1","pages":" 181-197"},"PeriodicalIF":3.5000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d4dt02721c?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02721c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0

Abstract

Metalation of dimesitylphosphane oxide, Mes2P(O)H (1), with alkali metal reagents (nBuLi, NaH, and A(hmds); A = K, Rb, and Cs) in THF yields the corresponding dimesitylphosphinites of lithium (2-thf), sodium (3-thf), potassium (4-thf), rubidium (5-thf), and caesium (6). Their molecular structures exhibit a broad and fascinating variety. Dinuclear compounds 2-thf, 3-thf, and 5-thf have central four-membered A2O2 rings, whereas the potassium congener crystallises as a tetranuclear complex with an inner A4O4 heterocubane cage. The tetranuclear caesium congener precipitates without thf coligands and exhibits a quite unique structure in its crystalline state. Due to their catalytic activity in hydrophosphorylation reactions, we focus on the solvent–structure relationship of the potassium derivatives. In hydrocarbons, [K4(O-PMes2)4]2 (4) is formed, and bidentate Lewis bases like dme and tmeda are unable to deaggregate this tetranuclear cage compound, but bases with a higher denticity (diglyme, triglyme, and pmdeta) split this cage compound into dinuclear complexes with central K2O2 rings. In addition, very bulky P-bound aryl groups like 2,4,6-triisopropylphenyl in dinuclear 8-thf hinder the formation of tetranuclear cage compounds, whereas 2-methylnaphthyl substituents are not bulky enough and the tetranuclear cage compound 7-thf is stabilised. For the 2,4,6-triisopropylphenyl substituent, the rubidium and caesium congeners 11 and 12 crystallise with two central A2O2 rings interconnected by π-interactions. A heteroleptic potassium complex 9-hmds, containing hmds as well as phosphinite anions, represents a snapshot on the way from the starting K(hmds) to the phosphinite-based heterocubane congener. Finally, heterobimetallic [{(thf)K}2Mg(O-PMes2)4] (10-thf) with tetrahedrally coordinated Mg centres has been isolated.

Abstract Image

碱金属二甲基亚砜配合物的合成和结构及其在氢化磷酸化反应中的催化活性
在四氢呋喃中用碱金属试剂(nBuLi、NaH、A(hmds);A = K、Rb、Cs)对二美斯膦氧化物 Mes2P(O)H (1) 进行金属化反应,可得到相应的锂(2-thf)、钠(3-thf)、钾(4-thf)、铷(5-thf)和铯(6)的二美斯膦酸盐。它们的分子结构呈现出广泛而迷人的多样性。2-thf、3-thf 和 5-thf 的二核化合物具有中心四元 A2O2 环,而钾同系物则结晶为内含 A4O4 杂古巴笼的四核复合物。四核铯同系物沉淀时没有thf配位体,其晶体结构非常独特。由于其在氢化磷酸化反应中的催化活性,我们将溶剂-结构关系的研究重点放在了钾衍生物上。在碳氢化合物[K4(O-PMes2)4]2 (4)中,双齿路易斯碱(如 dme 和 tmeda)无法分解这种四核笼状化合物,但具有较高齿度的碱(diglyme、triglyme、pmdeta)可将这种笼状化合物分割成具有中心 K2O2 环的双核复合物。此外,非常笨重的 P 键芳基(如二核 8-thf 中的 2,4,6-三异丙基苯基)会阻碍四核笼状化合物的形成,而 2-甲基萘取代基不够笨重,则会形成四核笼状化合物 7-thf。对于 2,4,6-三异丙基苯基取代基,铷和铯同系物 11 和 12 结晶为两个通过 π 相互作用相互连接的中心 A2O2 环。含有 hmds 和膦阴离子的杂多金属钾络合物 9-hmds 代表了从起始的 K(hmds)到基于膦的杂多古巴烷同系物过程中的一个缩影。最后,还分离出了具有四面体配位镁中心的杂多金属[{(thf)K}2Mg(O-PMes2)4](10-thf)。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信