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Reactivity of the Isolable Disilene R*PhSiSiPhR* (R*=Si t Bu 3 )
Author(s) -
Wiberg Nils,
Niedermayer Wolfgang,
Polborn Kurt,
Mayer Peter
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020617)8:12<2730::aid-chem2730>3.0.co;2-q
Subject(s) - cycloaddition , disilane , chemistry , reactivity (psychology) , adduct , medicinal chemistry , halogenation , silicon , stereochemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology
The disilene R*PhSiSiPhR* (R*=supersilyl=Si t Bu 3 ), which can be quantitatively prepared by dehalogenation of the disilane R*PhClSiSiBrPhR* with NaR* (yellow, water‐ and air‐sensitive crystals; decomp at ca. 70 °C; SiSi distance 2.182 Å), is comparatively reactive. It transforms 1) with Cl 2 , Br 2 , HCl, HBr, and HOH under 1,2‐addition into disilanes R*PhXSiSiX′PhR* (X/X′=Hal/Hal, H/Hal, H/OH), 2) with O 2 , S 8 , and Se n under insertion into 1,3‐disiletanes R*PhSi(Y) 2 SiPhR* (Y=O, S, Se), 3) with Me 2 CCH 2 under ene reaction into the disilane R*PhRSiSiHPhR* (R=CH 2 ‐CMeCH 2 ), 4) with N 2 O, Te n , t BuNC, and Me 3 SiNNN under [2+1] cycloaddition into disiliranes R*PhSiYSiPhR* (Y=O, Te, CN t Bu, NSiMe 3 ; P 4 adds 2 molecules of disilene), 5) with CO 2 , COS, PhCHO, and Ph 2 CS under [2+2] cycloaddition into disiletanes R*PhSiSiPhR*YCO (Y=O, S) as well as R*PhSiSiPhR*YCRPh (Y/R=O/H, S/Ph), 6) with CS 2 and CSe 2 under [2+3] cycloaddition into ethenes R* 2 Ph 2 Si 2 Y 2 C=CY 2 Si 2 Ph 2 R* 2 (Y=S, Se), and 7) with CH 2 CMeCMeCH 2 and Ph 2 CO under [2+4] cycloaddition into “Diels–Alder adducts”. X‐ray structure analyses of seven of these compounds are presented.