有机铟化合物的自组装现象

结合作者近两年来有机铟化合物自组装研究的一系列工作，综述了有机铟化合 物的自组装现象。有机铟化合物可以通过分子间的配位键和次级键连接而形成自组 装的二聚体或多聚体结构。其中一些有机铟化合物可以作为InN，InP，InAs的前体。     

LiCl‐Mediated Preparation of Functionalized Benzylic Indium(III) Halides and Highly Chemoselective Palladium‐Catalyzed Cross‐Coupling in a Protic Cosolvent

Sensitive functional groups such as COR, CHO, or CH₂OH can be present in benzylic indium reagents prepared by the direct insertion of indium in the presence of LiCl. These reagents undergo palladium‐catalyzed cross‐coupling reactions in the presence of a protic cosolvent after activation with iPrMgCl⋅LiCl (see scheme). Remarkable chemoselectivities are achieved by using various electrophiles containing NH or OH groups.

     

CsF als Fluoridierungsmittel für Organometall-Verbindungen der Elemente der Gruppe 13

CsF as Fluoridation Agent for Organometal Compounds of the Elements of Group 13 Cs[i-Bu₃AlF] ( 1 ) can be obtained by the reaction of Al(i-Bu)₃ with CsF in toluene. In a halide exchange reaction of Mes*GaCl₂ with CsF in acetonitrile not the desired product Mes*GaF₂ (Mes* = 2,4,6-(t-Bu)₃C₆H₂) was isolated but the metalate Cs[Mes*GaF₃] ( 2 ), formed by the addition of a third unit CsF. A ligand distribution was observed by the treatment of [(PhCH₂)₂GaTe(t-Bu)]₂ with CsF in THF. The triorganofluoro gallate [Cs{(PhCH₂)₃GaF}]₂ ( 3 ) was isolated. The triorganofluoro gallate Cs[Me₃GaF] does not react with dry O₂ in THF. With S₈ in THF a reaction was achieved and the diorganodifluoro gallate [Cs(THF)_0,5(Me₂GaF₂)] ( 4 ) could be characterized. The treatment of MesInBr₂ with CsF in acetonitrile gives as only identified compound the indate Cs[MesInBr₃] ( 5 ).     

Copper‐Catalyzed Coupling of Triaryl‐ and Trialkylindium Reagents with Aryl Iodides and Bromides through Consecutive Transmetalations

An efficient copper(I)‐catalyzed coupling of triaryl and trialkylindium reagents with aryl iodides and bromides is reported. The reaction proceeds at low catalyst loadings (2 mol %) and generally only requires 0.33 equivalents of the triorganoindium reagent with respect to the aryl halide as all three organic nucleophilic moieties of the reagent are transferred to the products through consecutive transmetalations. The reaction tolerates a variety of functional groups and sterically hindered substrates. Furthermore, preliminary mechanistic studies that entailed the synthesis and characterization of potential reaction intermediates offered a glimpse of the elementary steps that constitute the catalytic cycle.     

Synthesis and Characterization of Chiral Organogallium and Indium Complexes with Salen Ligands

Several new chiral organogallium and indium complexes with chiral Salen(1 and 2) as anxciliary ligands have been synthesized and characterized by elemental analysis,IR,^1H NMR and Mass spectroscopy.For the gallium,Mono and bimetallic complexes were obtained,whereas ring closure complexes of indium were obtained.     

铟试剂促进的水相化学反应及其在有机合成中的应用*

金属铟在空气中不会被氧化,在水中也很稳定,而且无毒,易被制成各种铟盐和有机铟试剂并参与化学反应。铟盐与其他Lewis酸相比也具有良好的水相稳定性。由于铟具有低的亲杂性,在反应过程中大多数官能团都不受影响,因而铟试剂成为有机合成中常用的导向试剂,受到了人们极大的关注。本文综述了近年来金属铟、铟盐及有机铟试剂参与的水相化学反应,介绍了铟试剂促进的一些新型反应的特点和优势及在有机合成中的应用,总结了水相中铟试剂参与化学反应的最新进展,提出了铟试剂今后研究和发展的重点和方向。     

Utilization of organogallium and organoindium compounds as alkylation reagents in organic synthesis: the addition of trialkylgallium and trialkylindium to aldehydes catalyzed by Lewis acids

The utilization of organogallium and organoindium compounds as alkylation reagents to aldehydes was realized with titanium tetrachloride as the strong Lewis acid catalyst. Furthermore, the catalytic asymmetric addition of organogallium to aldehydes was investigated with chiral titanium complexes, which were formed from titanium tetrachloride and salan ligands, with mediocre to good chemical yields and enantioselectivities. Copyright © 2005 John Wiley & Sons, Ltd.     

Einbau von Metallfluoriden in Organoindiumfluoride

Insertion of Metal Fluorides in Organoindium Fluorides . The reaction of i-Pr₂InCl ( 1 ) with CsF in acetonitrile at room temperature yields [(i-Pr₂InF)₅(CsF · 2 MeCN)] ([ 2 · 2 MeCN]). {[(MesInF₂)₁₀MgF₂] · 5 toluene} ({ 3 · 5 toluene}) can be isolated as a by-product in the reaction of Mes₃In with BF₃ · OEt₂ in the presence of MgBrCl. [ 2 · 2 MeCN] and { 3 · 5 toluene} were characterized by NMR spectroscopy as well as by X-ray structure determinations. [ 2 · 2 MeCN] forms infinite double chains of (i-Pr₂InF)₅-blocks and CsF-units. The coordination sphere of the cesium atom consists of three fluorine atoms and the nitrogen atoms of three acetonitrile molecules, which wrap the metal atom in a strongly distorted octahedral fashion. One of the acetonitrile molecules in [ 2 · 2 MeCN] has a μ₂-bridging function. This results in the formation of four membered Cs₂N₂-rings. In { 3 · 5 toluene}, ten molecules of MesInF₂ are forming a cage in which a linear MgF₂-unit is inserted.     

Useful and accessible organometallic precursors for preparation of zinc sulfide and indium sulfide thin films via solution pyrolysis (printing) method

Polycrystalline β-zinc sulfide thin films were prepared by solution pyrolysis of an ethylzinc isopropylthiolate–zinc bis(dibutyldithiocarbamate) combined precursor (EtZnSiPr–Zn(S₂CNnBu₂)₂) in chloroform solution on glass or silicon(111) substrates at 300°C. Homogeneous but amorphous indium sulfide thin films were obtained from butylindium bis(isopropylthiolate) (nBuInSiPr₂) in P-xylene on these substrates at 300°C similarly. The sulfide thin films obtained were characterized by means of X-ray photoelectron spectroscopy (XPS), X-ray fluorescence Microanalysis, scanning electron microscopy (SEM) and optical band gap measurements.