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Diradicaloid or Zwitterionic Character: The Non‐Tetrahedral Unsaturated Compound [Si 4 {N(SiMe 3 )Dipp} 4 ] with a Butterfly‐type Si 4 Substructure

2017; Wiley; Volume: 56; Issue: 44 Linguagem: Inglês

10.1002/anie.201705787

1521-3773

Jan Keuter, Kevin Schwedtmann, Alexander Hepp, Klaus Bergander, Oliver Janka, Carsten Doerenkamp, Hellmut Eckert, Christian Mück‐Lichtenfeld, Felicitas Lips,

Coordination Chemistry and Organometallics

Abstract The reduction of the tribromoamidosilane {N(SiMe 3 )Dipp}SiBr 3 (Dipp=2,6‐ i Pr 2 C 6 H 3 ) with potassium graphite or magnesium resulted in the formation of [Si 4 {N(SiMe 3 )Dipp} 4 ] ( 1 ), a bicyclo[1.1.0]tetrasilatetraamide. The Si 4 motif in 1 does not adopt a tetrahedral substructure and exhibits two three‐coordinate and two four‐coordinate silicon atoms. The electronic situation on the three‐coordinate silicon atoms is rationalized with positive and negative polarization based on EPR analysis, magnetization measurements, and DFT calculations as well as 29 Si CP MAS NMR and multinuclear NMR spectroscopy in solution. Reactivity studies with 1 and radical scavengers confirmed the partial charge separation. Compound 1 reacts with sulfur to give a novel type of silicon sulfur cage compound substituted with an amido ligand, [Si 4 S 3 {N(SiMe 3 )Dipp} 4 ] ( 2 ).