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Versatile Conversion of N ‐Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal–Carbon and Metal–Hydrogen Bonds
Author(s) -
Xiong Yun,
Yao Shenglai,
Driess Matthias
Publication year - 2012
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.201103656
Subject(s) - silylene , chemistry , silylation , metal , silicon , zinc , medicinal chemistry , insertion reaction , divalent metal , molar ratio , crystallography , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry , catalysis
The facile one‐pot reaction of the stable N ‐heterocyclic silylene LSi: 1 (L(ArN)C(CH 2 ) CHC(Me)(NAr), Ar=2,6‐ i Pr 2 C 6 H 3 ) with Me 2 Zn, Me 3 Al, H 3 Al‐NMe 3 , and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding MC and AlH bonds under very mild reaction conditions. Thus, Me 2 Zn furnishes the bis(silyl) zinc complex LSi(Me)ZnSi(Me)L 2 as the sole product, irrespective of the molar ratio of the starting materials applied. Moreover, the reactions of 1 with Me 3 Al, H 3 Al‐NMe 3 , and MeLi lead directly to the 1,1‐addition products LSi(Me)(Al(thf)Me 2 ) 3 , LSi(H)(AlH 2 (NMe 3 )) 4 , and LSi(Me)Li(thf) 3 5 , respectively. All new compounds 2 – 5 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single‐crystal X‐ray diffraction analyses.