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  3. 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
10.48350/178523
Publisher DOI
10.1002/chem.202201716
PubMed ID
35775467
Abstract
Rare examples of heavier alkali metal manganates [{(AM)Mn(CH2 SiMe3 )(N'Ar )2 }∞ ] (AM=K, Rb, or Cs) [N'Ar =N(SiMe3 )(Dipp), where Dipp=2,6-iPr2 -C6 H3 ] 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 [(Et2 O)2 Na(n Bu)Mn[(N'Ar )2 ], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium.
Date Issued
2022-07-01
Publication Type
Article
Subject(s)
500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
000 Computer science, knowledge & systems
Language(s)
en
Author(s)
Ballmann, Gerd M.
Gentner, Thomas X.
Kennedy, Alan R.
Hevia Freire, Eva  
Departement für Chemie, Biochemie und Pharmazie (DCBP) Universität Bern  
Mulvey, Robert E.
Additional Credits
Departement für Chemie, Biochemie und Pharmazie (DCBP) Universität Bern  
Journal
Chemistry – A European Journal
Publisher
European Chemical Societies Publishing
ISSN
0947-6539
Access(Rights)
open.access
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