Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent-Induced Dissociation Effects.
Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent-Induced Dissociation Effects.
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DOI：
10.1002/chem.202201716
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发表时间：
2022-10-04
影响因子：
4.3
通讯作者：
Mulvey, Robert E.
中科院分区：
文献类型：
--
作者：
Ballmann, Gerd M.;Gentner, Thomas X.;Kennedy, Alan R.;Hevia, Eva;Mulvey, Robert E.
较重的碱金属锰酸盐[{（AM）Mn（CH 2SiMe 3）（N 'Ar）2}∞]（AM=K、Rb或Cs）[N' Ar =N（SiMe 3）（Dipp），其中Dipp= 2，6-iPr 2-C6 H3]的稀有实例已经合成，其中Rb和Cs实例进行晶体学表征。这些最重的锰酸盐结晶为聚合物之字形链，通过AM-β-π-芳烃相互作用传播。其制备的关键是避免使用刘易斯碱供体溶剂。相比之下，使用多齿氮供体鼓励配体混乱，导致这些双金属化合物重新分配为其相应的同金属物种，如完整的Li-Cs系列所证明的。除了少数已知的晶体学表征的非溶剂化和溶剂化的铷和铯s-区金属酰胺，六种新的衍生物（[{AM（N 'Ar）}∞]，[{AM（N' Ar）<$TMEDA}∞]和[{AM（N 'Ar）<$PMDETA}∞]，其中AM=Rb或Cs）已被结构鉴定。利用单齿二乙醚作为供体，也可以分离和结晶学上分离钠离子[（Et 2 O）2Na（nBu）Mn[（N 'Ar）2]，这是一种单体双核结构，通过与钠结合的两个封闭醚配体防止聚集。 当不存在给体溶剂时，重碱金属烷基可以与锰双（酰胺）形成盐化合物，但是引入共同的给体TMEDA或PMDETA导致盐的分解以及配体交换，这导致形成新的溶剂化的重碱金属酰胺和烷基锰酰胺。
Rare examples of heavier alkali metal manganates [{(AM)Mn(CH2SiMe3)(N‘Ar)2}∞] (AM=K, Rb, or Cs) [N‘Ar=N(SiMe3)(Dipp), where Dipp=2,6‐iPr2‐C6H3] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig‐zag chains propagated by AM⋅⋅⋅π‐arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li ‐ Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s‐block metal amides, six new derivatives ([{AM(N‘Ar)}∞], [{AM(N‘Ar)⋅TMEDA}∞], and [{AM(N‘Ar)⋅PMDETA}∞] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et2O)2Na( n Bu)Mn[(N‘Ar)2], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium. Heavy alkali metal alkyls can form ate compounds with manganese bis(amides) when donor solvents are absent but introducing the common donors TMEDA or PMDETA leads to breakdown of the ates together with ligand exchange, which results in the formation of new solvated heavier alkali metal amides and alkylmanganese amides.
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影响因子：
16.6
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影响因子：
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