The Weakly Coordinating Tris(trichlorosilyl)silyl Anion.
Angew Chem Int Ed Engl
; 56(52): 16490-16494, 2017 12 22.
Article
in En
| MEDLINE
| ID: mdl-29149501
ABSTRACT
Closely following the procedure for the preparation of the base-stabilized dichlorosilylene complex NHCDipp â
SiCl2 reported by Roesky, Stalke, and co-workers (Angew. Chem. Int. Ed. 2009, 48, 5683-5686), a few crystals of the salt [NHCDipp -Hâ
â
â
Clâ
â
â
H-NHCDipp ]Si(SiCl3 )3 were isolated, aside from the reported byproduct [NHCDipp -H+ â
â
â
Cl- ], and characterized by X-ray crystallography (NHCDipp =N,N-di(2,6-diisopropylphenyl)imidazo-2-ylidene). They contain the weakly coordinating anion Si(SiCl3 )3- , which was also obtained in high yields upon deprotonation of the conjugate Brønsted acid HSi(SiCl3 )3 with NHCDipp or PMP (PMP=1,2,2,6,6-pentamethylpiperidine). The acidity of HSi(SiCl3 )3 was estimated by DFT calculations to be substantially higher than those of other H-silanes. Further DFT studies on the electronic structure of Si(SiCl3 )3- , including the electrostatic potential and the electron localizability, confirmed its low basicity and nucleophilicity compared with other silyl anions.
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MEDLINE
Language:
En
Year:
2017
Type:
Article