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Striking Reactivity of a Stable, Zwitterionic Silylene Towards Substituted Diazomethanes, Azides, and Isocyanides
Author(s) -
Xiong Yun,
Yao Shenglai,
Driess Matthias
Publication year - 2009
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/chem.200901337
Subject(s) - silylene , isocyanide , reactivity (psychology) , yield (engineering) , chemistry , trimethylsilyl azide , silylation , trimethylsilyl , medicinal chemistry , cyanide , trimethylsilyl cyanide , azide , nuclear magnetic resonance spectroscopy , crystallography , stereochemistry , organic chemistry , silicon , catalysis , materials science , medicine , alternative medicine , pathology , metallurgy
The reactivity of the zwitterionic N‐heterocyclic silylene (NHS) LSi: 1 (L=ArNC(Me)CHC(CH 2 )NAr, Ar=2,6‐ i Pr 2 C 6 H 3 ), towards diphenyldiazomethane (Ph 2 CN 2 ), trimethylsilyl azide (Me 3 SiN 3 ), and cyclohexyl isocyanide (C 6 H 11 NC) is reported. The addition of Ph 2 CN 2 to 1 leads to the diiminylsilane LSi(NCPh 2 ) 2 2 (80 % yield), whereas the treatment of 1 with Me 3 SiN 3 gives the spirobicyclic silatetrazoline LSi(NNSiMe 3 ) 2 3 (67 % yield), and addition of C 6 H 11 NC gives the silyl cyanide LSi(R)CN (R=cyclohexyl) 4 (32 % yield) along with the unexpected azasilacyclobutane 5 (41 % yield). The novel compounds were fully characterized by 1 H, 13 C, and 29 Si NMR spectroscopy, ESIMS, elemental analysis, and single‐crystal X‐ray diffraction.