REACTIONS OF H(PHMESI)(3)H WITH TRIFLIC ACID - EVIDENCE FOR REARRANGEMENT PROCESSES

Citation
Jy. Corey et al., REACTIONS OF H(PHMESI)(3)H WITH TRIFLIC ACID - EVIDENCE FOR REARRANGEMENT PROCESSES, Organometallics, 13(9), 1994, pp. 3408-3410
Citations number
29
Language
INGLESE
art.tipo
Note
Categorie Soggetti
Chemistry Inorganic & Nuclear","Chemistry Inorganic & Nuclear
Journal title
ISSN journal
0276-7333
Volume
13
Issue
9
Year of publication
1994
Pages
3408 - 3410
Database
ISI
SICI code
0276-7333(1994)13:9<3408:ROHWTA>2.0.ZU;2-4
Abstract
The reaction of the trisilane, H(PhMeSi)(3)H, with 1 or 2 equiv of tri flic acid (HOTf) followed by quenching with MeMgBr resulted in the for mation of two isomers each of Ph(2)Me(4)Si(3)H(2) and PhMe(5)Si(3)H(2) , respectively. When H(PhMeSi)(3)H was treated with 3 equiv of triflic acid and quenched with PhMgBr, two isomers of Ph(3)Me(3)Si(3)H(2) wer e formed. The isomers formed in the sequence with 1 equiv of HOTf resu lt from competitive cleavage of internal SiPh bonds vs terminal SiPh b onds, as demonstrated by labeling experiments. The products formed fro m reaction with a second and third equivalent of trific acid require a rearrangement process and may be rationalized through a common cation ic intermediate, [HMe(TfO)SiSiMesi(X)MeH](+) OTf(-) (X = Ph, OTf).