Preparation and Characterization of Tris(trimethylsilyl)germylzinc Chloride and Bis[tris(trimethylsilyl)germyl]zinc
作者:Masato Nanjo、Takashi Oda、Kunio Mochida
DOI:10.1246/cl.2002.108
日期:2002.1
The germylzinc chloride 1 has a dimeric structure consisting of two μ-Cl atoms. The compound 1 reacted with (Me3Si)3GeLi in diethyl ether to give [(Me3Si)3Ge]2Zn (2), quantitatively. The structure of bis(germyl)zinc 2 has been also elucidated by X-ray diffraction.
(Me3Si)3GeZnCl (1) 的分子结构已通过单晶 X 射线衍射确定。锗基氯化锌1具有由两个μ-Cl原子组成的二聚体结构。化合物1在乙醚中与(Me3Si)3GeLi反应,定量得到[(Me3Si)3Ge]2Zn(2)。双(锗基)锌 2 的结构也已通过 X 射线衍射阐明。
Deposition of metal films based upon complementary reactions
申请人:WAYNE STATE UNIVERSITY
公开号:US09540730B2
公开(公告)日:2017-01-10
A method comprises contacting a compound having formulae (1) with a compound having formula MLo to form a metal:
[M(SiR3)m(L1)p]n (1)
wherein
M is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, a second row transition metal or a third row transition metal;
R are each independently H, C1-C6 alkyl or —Si(R″)3;
R″ are each independently H or C1-C6 alkyl;
m is an integer from 1 to 3;
n is a number representing the formation of aggregates or polymeric material;
L1 is a neutral donor ligand;
L is a ligand;
p is an integer from 0 to 6; and
o is an integer representing the number of ligands bonded to MLo.
Development of a Radical Silylzincation of (Het)Aryl‐Substituted Alkynes and Computational Insights into the Origin of the
<i>trans</i>
‐Stereoselectivity
Aryl- and hetaryl-substituted acetylenes undergo regio- and stereoselective silylzincation by reaction with [(Me3Si)3Si]2Zn in the presence of Et2Zn (10–110 mol%) as additive. The distinctive feature of this addition across the C−C triple bond is its trans stereoselectivity. The radical nature of the silylzincation process is supported by diagnostic experiments and DFT calculations, which also corroborate
stereoretentive copper(I)-mediated electrophilic substitution of the intermediate C(sp2)–Zn bond. These stereodivergent protocols offer a regio- and stereoselective access to trisubstituted vinylsilanes decorated with sulfur-, oxygen-, and phosphorus substituents with either double-bond geometry. Sulfur-, oxygen-, and phosphorus-substituted terminalalkynes undergo regio- and stereoselective silylzincation
SiHbonds can be activated by organozinc and silylzinc compounds in the presence of minute amounts of radical initiators such as tBu2Hg or AIBN, yielding zinciosilanes in good yields (see scheme). Activation of dihydridosilanes leads to geminal dizinciosilanes. Zincio‐bridged disilyllithium compounds, which have three (1) and four metal–silicon bonds, were also synthesized.