Versatile Conversion of N-Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal-Carbon and Metal-Hydrogen Bonds

被引:29
|
作者
Xiong, Yun [1 ]
Yao, Shenglai [1 ]
Driess, Matthias [1 ]
机构
[1] Tech Univ Berlin, Inst Chem Metalorgan & Inorgan Mat, D-10623 Berlin, Germany
关键词
dimethyl zinc; lithium; metal silanide; metalation; trimethylaluminum; YLIDE-LIKE SILYLENE; X-RAY CRYSTAL; STABLE SILYLENE; REACTIVITY; ACTIVATION; DERIVATIVES; COMPLEXES; CHEMISTRY; ADDUCTS; LIGAND;
D O I
10.1002/chem.201103656
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The facile one-pot reaction of the stable N-heterocyclic silylene LSi: 1 (L?(ArN)C(?CH2) CH?C(Me)(NAr), Ar=2,6-iPr2C6H3) with Me2Zn, Me3Al, H3Al-NMe3, and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding M?C and Al?H bonds under very mild reaction conditions. Thus, Me2Zn 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 Me3Al, H3Al-NMe3, and MeLi lead directly to the 1,1-addition products LSi(Me)(Al(thf)Me2) 3, LSi(H)(AlH2(NMe3)) 4, and LSi(Me)Li(thf)3 5, respectively. All new compounds 25 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.
引用
收藏
页码:3316 / 3320
页数:5
相关论文
共 50 条
  • [41] Functionalization of Carbon-Hydrogen Bonds Through Transition Metal Carbenoid Insertion
    Davies, Huw M. L.
    Dick, Allison R.
    C-H ACTIVATION, 2010, 292 : 303 - 345
  • [42] Insertion of SO2 into the metal-carbon bonds of rhodium and iridium compounds, and reactivity of the SO2-inserted species
    Lefort, L
    Lachicotte, RJ
    Jones, WD
    ORGANOMETALLICS, 1998, 17 (07) : 1420 - 1425
  • [43] Reactions of Oxygen with Metallaheterocyclic Alkyl Amide Complexes. Selective Insertion of Oxygen into Metal-Carbon Bonds
    Yu, Xianghua
    Chen, Xue-Tai
    Xue, Zi-Ling
    ORGANOMETALLICS, 2009, 28 (23) : 6642 - 6645
  • [44] FORMATION OF METAL-CARBON BONDS VIA INSERTION REACTIONS IN GASEOUS NEGATIVE ION-MOLECULE REACTIONS
    BAUMGARTNER, E
    RHYNE, TC
    DILLARD, JG
    JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1979, 171 (03) : 387 - 398
  • [45] COMPLEXES WITH METAL-CARBON BONDS, .3. PREPARATION AND PROPERTIES OF BINUCLEAR DIARYLPLATINUM(II) COMPOUNDS
    STEELE, BR
    VRIEZE, K
    TRANSITION METAL CHEMISTRY, 1977, 2 (04) : 140 - 144
  • [46] Three Ag(I)-cyanide coordination polymers with metal bonds tuned by N-heterocyclic ligands
    Shao, Min
    Li, Ming-Xing
    Wang, Xue-Qin
    Zhang, Heng-Hua
    INORGANIC CHEMISTRY COMMUNICATIONS, 2015, 61 : 10 - 12
  • [47] Cobalt-Catalyzed Regioselective Borylation of Arenes: N-Heterocyclic Silylene as an Electron Donor in the Metal-Mediated Activation of C-H Bonds
    Ren, Hailong
    Zhou, Yu-Peng
    Bai, Yunping
    Cui, Chunming
    Driess, Matthias
    CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (24) : 5663 - 5667
  • [48] ION-BEAM STUDIES OF THE REACTIONS OF ATOMIC COBALT IONS WITH ALKANES - DETERMINATION OF METAL-HYDROGEN AND METAL-CARBON BOND-ENERGIES AND AN EXAMINATION OF THE MECHANISM BY WHICH TRANSITION-METALS CLEAVE CARBON-CARBON BONDS
    ARMENTROUT, PB
    BEAUCHAMP, JL
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (04) : 784 - 791
  • [49] STERIC EFFECTS OF TERTIARY PHOSPHINES ON NUCLEOPHILE-INDUCED INSERTION OF CARBON-MONOXIDE INTO TRANSITION METAL-CARBON BONDS
    COTTON, JD
    MARKWELL, RD
    INORGANICA CHIMICA ACTA-ARTICLES, 1982, 63 (01): : 13 - 16
  • [50] The Catalytic Role of N-Heterocyclic Carbene in a Metal-Free Conversion of Carbon Dioxide into Methanol: A Computational Mechanism Study
    Huang, Fang
    Lu, Gang
    Zhao, Lili
    Li, Haixia
    Wang, Zhi-Xiang
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (35) : 12388 - 12396