Crystal and Molecular Structure of Manganese(II) Lapacholate, a Novel Polymeric Species Undergoing Temperature-Reversible Metal to Ligand Electron Transfer

2009 ◽  
Vol 48 (8) ◽  
pp. 3529-3534 ◽  
Author(s):  
Francesco Caruso ◽  
Miguel A. Martínez ◽  
Miriam Rossi ◽  
Alexander Goldberg ◽  
M. Elizabeth Chacón Villalba ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Electron Transfer ◽  
Crystal And Molecular Structure ◽  
Polymeric Species

Elektronenreiche Olefine, 2 Struktur und Elektrontransfer-Reaktivität des cyclisch σ/π-hyperkonjugierten Carbosilans 3,3,6,6-Tetrakis(trimethylsilyl)-1,4-cyclohexadien

1988 ◽  
Vol 43 (9) ◽  
pp. 1087-1093 ◽  
Author(s):  
Hans-Dieter Hausen ◽  
Christian Bessenbacher ◽  
Wolfgang Kaim
Keyword(s):  
Molecular Structure ◽  
Electron Transfer ◽  
Transfer Reaction ◽  
Crystal And Molecular Structure ◽  
Cation Radical ◽  
Electron Transfer Reaction ◽  
Boat Conformation ◽  
Single Electron Transfer ◽  
Molecular Structure Analysis ◽  
Single Electron Transfer Reaction

Abstract Crystal and molecular structure analysis of the title compound 1, a most electron rich carbosilane, exhibits a shallow boat conformation for the cyclohexadiene ring which is shielded by four bulky Me3Si groups. Multiple hyperconjugative interaction occurs between the two non-conjugated olefinic π systems and the four rather long (192 pm) carbon-silicon o bonds which form an angle of about 34° with the assumed π axis. The HOMO destabilization caused by this unique structural arrangement explains the energetically facile formation and subsequent reactivity of the cation radical 1+ which was found to undergo oxidative desilylation to the aromatic 1,4-bis(trimethylsilyl) benzene precursor in the single electron transfer reaction with TCNE.

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