The First Isolable 1,1-Dilithiogermane and Its Unusual Dimeric Structure-An Effective Reagent for the Preparation of Double-Bonded Derivatives of Group 14 Elements
Heavy cyclopropene analogues R4SiGe2 and R4Ge3 (R = SiMe Bu2) – New members of the cyclic digermenes family
作者:Vladimir Ya. Lee、Hiroyuki Yasuda、Masaaki Ichinohe、Akira Sekiguchi
DOI:10.1016/j.jorganchem.2006.03.049
日期:2007.1
1H-Siladigermirene R4SiGe2 (2a) and 1H-trigermirene R4Ge3 (2b) (R = SiMe'Bu,) with a Ge=Ge double bond were synthesized by the reaction of tetrachlorodigermane RGeCl2-GeCl2R with dilithiosilane R2SiLi2 and dilithiogermane R2GeLi2, respectively. The skeletal Ge=Ge double bond of 2a is trans-bent (51.0(2)degrees) with a bond distance of 2.2429(6) angstrom. The reaction of both 2a and 2b with CH2Cl2 resulted in the formation of unusual four-membered ring compounds 5a and 5b as a result of a ring expansion reaction. 1H-Trisilirene 7a and 3H-disilagermirene 7b with an Si=Si double bond also smoothly reacted with CH2Cl2 to yield the four-membered ring systems 8a and 8b, respectively. (c) 2006 Elsevier B.V. All rights reserved.
A Schrock-Type Germylene Complex: (η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>Et)<sub>2</sub>(PMe<sub>3</sub>)Hf═Ge(SiMe<sup>t</sup>Bu<sub>2</sub>)<sub>2</sub>
作者:Norio Nakata、Shinji Aoki、Vladimir Ya. Lee、Akira Sekiguchi
DOI:10.1021/om501134a
日期:2015.6.8
The stable group 4 metal germylene complex (eta(5)-C5H4Et)(2)(PMe3)Hf=Ge((SiMeBu2)-Bu-t)(2) (2) is readily available by the reaction of the 1,1-dilithiogermane ((Bu2MeSi)-Bu-t)(2)GeLi2 with (eta(5)-C5H4Et)(2)HfCl2 in toluene at -50 degrees C, followed by treatment with trimethylphosphine. The hafnium-germanium bond distance of 2.6705(5) angstrom in 2 is indicative of its double-bond character, being ca. 3-7% shorter than the usual Hf-Ge single bonds. The novel hafnium germylene derivative is classified as a Schrock-type complex, featuring a negatively polarized nucleophilic germanium center.