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

IF 4.3 3区 材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC ACS Applied Electronic Materials Pub Date : 2024-10-30 DOI:10.1039/d4dt02721c
Benjamin Fener, Philipp Schüler, Phil Liebing, Helmar Görls, Matthias Westerhausen
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引用次数: 0

摘要

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)。
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Syntheses and Structures of Dimesitylphosphinite Complexes of the Alkali Metals as well as Their Catalytic Activity in Hydro-phosphorylation Reactions
Metalation of dimesitylphosphane oxide, Mes2P(O)H (1), with alkali metal reagents (nBuLi, NaH, A(hmds); A = K, Rb, 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. The dinuclear compounds 2-thf, 3-thf, and 5-thf have central four-membered A2O2 rings, whereas the potassium congener crystallises as tetranuclear complex with an inner A4O4 heterocuban cage. The tetranuclear caesium congener precipitates without thf coligands and exhibits a quite unique structure in its crystalline state. Due to its catalytic activity in hydrophosphorylation reactions, we focus the solvent-structure relationship on the potassium derivatives. In hydrocarbons, [K4(O-PMes2)4]2 (4) forms, bidentate Lewis bases like dme and tmeda are unable to deaggregate this tetranuclear cage compound, but bases with a higher denticity (diglyme, triglyme, 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 forms. 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 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.
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