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.

引用

页码：15899 / 15904

页数：6

共 93 条

[1] Stabilization of the Heavy Methylene Analogues, GeH2 and SnH2, within the Coordination Sphere of a Transition Metal [J].

Al-Rafia, S. M. Ibrahim ;

Malcolm, Adam C. ;

Liew, Sean K. ;

Ferguson, Michael J. ;

Rivard, Eric .

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 [J].

Arii, Hidekazu ;

Amari, Taiyo ;

Kobayashi, Junji ;

Mochida, Kunio ;

Kawashima, Takayuki .

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 [J].

Asay, Matthew ;

Jones, Cameron ;

Driess, Matthias .

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 [J].

Bibal, C ;

Mazières, S ;

Gornitzka, H ;

Couret, C .

ORGANOMETALLICS, 2002, 21 (14) :2940-2943

[10] Stable carbenes [J].

Bourissou, D ;

Guerret, O ;

Gabbaï, FP ;

Bertrand, G .

CHEMICAL REVIEWS, 2000, 100 (01) :39-91

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