Synthesis of Dichlorogallane HGaCl₂

Abstract

The product is a light-to dark-brown solid depending on its grain size; it is sensitive to moisture and is practically insoluble in all the common organic solvents. In contrast to the nitrosyl chlorides of iron [ l ] and cobalt [2], the new compound cannot be sublimed and is therefore probably polymeric in nature. Its infrared spectrum in Nujol contains N-0 absorptions at 1924 (s), 1761 (vs) cm-1 [3] plus two bands at 309 and 261 cm-1 which can be assigned to V-CI stretching vibrations. Comparison of the infrared spectrum with those of other nitrosylmetal chlorides [3] showed that [V(N0)3C12In has probably a polynuclear structure (1) with terminal a n d bridging chloro ligands. This structure contains sixfold coordinated vanadium with an inert-gas configuration 45.5 35/1 [a1 16.5 34-35/3 16.0 57-5813 40.0 [b] 45/1.5 [a]and has a trigonal bipyramidal arrangement of the N O groups; these features are in agreement with the fact that the compound is diamagnetic and gives only two N -0 absorptions in the infrared. Received: December 15th, 1964 [Z 880/701 IE] German version: Angew. Chem. 77, 134 (1965) [I] W.Trimethylsilane reacts a t -20 O C with equimolar amounts of gallium trichloride to form trimethylchlorosilane (99.5 "/: yield) and pure dichlorogallane.(H3C)3SiH + GaC13 + (H3C)3SiCI + HGaC12When the chlorosilane is pumped off at -30 OC, a residue of HGaC12 is obtained in 95 % yield as colorless crystals which dissolve well and without decomposition a t low temperatures in anhydrous solvents such as benzene, cyclohexane, or diethyl ether [l].

X-RAY CRYSTAL STRUCTURE OF AN ORGANOINDIUM ALKOXIDE DIMER, (Ph2InOSiMe3)2

“…Toluene and benzene-d 6 were distilled from sodium/benzophenone ketyl under dry dinitrogen. P(SiMe 3 ) 3 The title compound was prepared via the adventitious hydrolysis of a reaction mixture containing P(SiMe 3 ) 3 Table II; selected distances and angles are provided in Table III.…”

“…3 Although a variety 0 of organoindium alkoxides have been fabricated for use in relation to these 0 CMe 3 , 6 CPh 3 , 7 Me, 8 CD 3 , 9 t-Bu' 0 : R = CD 3 ; R' = Me, CD 3 : 9 R = Et; R' = Me, Et 9 R = Bu; R' = Bu, Phnl). The nature of these compounds was established by a combination of NMR spectroscopy, cryoscopic molecular weight determination, and infrared techniques.…”

Convenient Access to Gallium(I) Cations through Hydrogen Elimination from Cationic Gallium(III) Hydrides

“…Hydrosilanes have long been known to convert chlorogallanes into hydrogallanes at or below room temperature, as according to eq It is likely that residual Et 3 SiH from the synthesis of the silylium ion reagent [Et 3 Si]­[CHB 11 Cl 11 ] caused the formation of an intermediate [H 2 Ga] + ion, which then eliminated H 2 to afford compound 1 .…”

“…As this finding was supported by preliminary DFT calculations, which indicated that the Hydrosilanes have long been known to convert chlorogallanes into hydrogallanes at or below room temperature, as according to eq 2. 20…”

Gallium Hydrides with a Radical-Anionic Ligand

“…The gallium hydrides are extensively explored within the Group 13 metals hydride chemistry. − These compounds attract a significant attention in terms of their practical application and fundamental aspects. For instance, volatile Lewis acid–base adducts of GaH 3 and some related hydridogallium derivatives are considered as potential easy-to-handle sources for preparation of GaN and GaAs films or nanoparticles in MOCVD processes. ,− Also, dichlorogallane Cl 2 GaH, − dialkyl-, − and diarylgallanes − react with unsaturated substrates (ketones, nitriles, olefins, and alkynes) by addition of the Ga–H bond across the multiple bond to result in hydrogallation products. ,,,− Hydrometalation reactions of substituted alkynes by dichloro- or dialkylgallanes have been investigated in detail, and the diversity of the reactions pathways and the frameworks of the formed gallium-containing compounds were shown. ,− Sometimes, hydrogallation reactions proceed more selectively compared to hydroalumination processes. , …”