A Germylene Stabilized by Homoconjugation

被引：36
作者：
Dong, Zhaowen [1 ]
Reinhold, Crispin R. W. [1 ]
Schmidtmann, Marc [1 ]
Mueller, Thomas [1 ]
机构：
[1] Carl von Ossietzky Univ Oldenburg, Inst Chem, Carl von Ossietzky Str 9-11, D-26129 Oldenburg, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 51期
关键词：
carbene analogues; germanium; homoconjugation; hyperconjugation; X-ray diffraction; TRANSITION-METAL-COMPLEXES; NATURAL RESONANCE THEORY; INITIO SCF-MO; CATIONIC METALLOGERMYLENE; INVERTED SEQUENCE; CRYSTAL-STRUCTURE; ELEMENTS; CHEMISTRY; REACTIVITY; AMIDES;
D O I：
10.1002/anie.201609576
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The synthesis of a bicyclic germylene from the reaction of a germole dianion with hafnocene dichloride is reported. This germylene is stabilized by a homoconjugative interaction of the dicoordinated germanium atom with a remote C=C double bond. First reactivity studies revealed its nucleophilic character and resulted in the synthesis of bimetallic hafnium/iron and hafnium/tungsten complexes with a germylene group linker.
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收藏
页码：15899 / 15904
页数：6
相关论文
共 93 条
  • [1] Stabilization of the Heavy Methylene Analogues, GeH2 and SnH2, within the Coordination Sphere of a Transition Metal
    Al-Rafia, S. M. Ibrahim
    Malcolm, Adam C.
    Liew, Sean K.
    Ferguson, Michael J.
    Rivard, Eric
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (04) : 777 - 779
  • [2] [Anonymous], 2011, QTAIM ANAL WAS PERFO
  • [3] [Anonymous], ANGEW CHEM
  • [4] Arii H., 2012, ANGEW CHEM, V124, P6842
  • [5] Low-Coordinate Germanium(II) Centers Within Distorted Axially Chiral Seven-Membered Chelates: Stereo- and Enantioselective Cycloadditions
    Arii, Hidekazu
    Amari, Taiyo
    Kobayashi, Junji
    Mochida, Kunio
    Kawashima, Takayuki
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (27) : 6738 - 6741
  • [6] N-Heterocyclic Carbene Analogues with Low-Valent Group 13 and Group 14 Elements: Syntheses, Structures, and Reactivities of a New Generation of Multitalented Ligands
    Asay, Matthew
    Jones, Cameron
    Driess, Matthias
    [J]. CHEMICAL REVIEWS, 2011, 111 (02) : 354 - 396
  • [7] Bader R. F. W., 1994, ATOMS MOL QUANTUM TH
  • [8] Bender JE, 1997, ORGANOMETALLICS, V16, P2743
  • [9] From chlorogermylenes to stable hydroxy- and siloxy-germylene-tungsten complexes
    Bibal, C
    Mazières, S
    Gornitzka, H
    Couret, C
    [J]. ORGANOMETALLICS, 2002, 21 (14) : 2940 - 2943
  • [10] Stable carbenes
    Bourissou, D
    Guerret, O
    Gabbaï, FP
    Bertrand, G
    [J]. CHEMICAL REVIEWS, 2000, 100 (01) : 39 - 91
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