Gallane: synthesis, physical and chemical properties, and structure of the gaseous molecule Ga2H6 as determined by electron diffraction

Pulham, Colin R.; Downs, Anthony J.; Goode, Michael J.; Rankin, David W. H.; Robertson, Heather E.

doi:10.1021/ja00014a003

Cited by 157 publications

(186 citation statements)

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“…These frequencies are close to 1976 and 1993 cm -1 reported in Ref. [9] for Ga 2 H 6 vapor. As follows from drogenation of adsorbed ethyl species which is also confirmed by appearance of the weak C-H stretching band at 3046 cm -1 that should be ascribed to the stretching vibrations of CH 2 groups in resulting ethylene (Fig.…”

Section: Resultssupporting

confidence: 88%

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

et al. 2006

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The present study reports an unusual diffuse reflection Fourier transform (DRIFT) spectrum of ethane adsorbed by gallium oxide. One of the stretching C-H bands in this spectrum with a maximum at 2753 cm -1 is more than by 100 cm -1 shifted toward lower frequencies in comparison with gaseous ethane. In addition, the relative intensity of this band is unusually high. This indicates a very strong polarizability of the corresponding chemical bonds resulting from perturbation of ethane by the low coordinated Ga 3+ cations. The assignment of this band to the very strongly perturbed initially fully symmetric ν 1 C-H stretching vibration is confirmed by a DFT modeling of ethane adsorption by the simplest Ga 2 O 3 cluster. The obtained results also indicate heterolytic dissociative adsorption and dehydrogenation of ethane by Ga 3+ Lewis sites at elevated temperature. This is evidenced by appearance of new IR bands from gallium alkyl fragments and acidic protons followed by decomposition of resulting gallium ethyl species. In parallel, the most intense IR band at lower frequency from the most strongly polarized C-H chemical bond decreased in intensity. The obtained results indicate that these vibrations are involved in subsequent heterolytic dissociative adsorption. The obtained results demonstrate that, similar to the shifts of C-H stretching vibrations to the low-frequency, intensities of IR C-H stretching bands can be also used as an index of chemical activation of adsorbed paraffins via their polarization by the low-coordinated cations.

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Section: Resultssupporting

confidence: 88%

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

et al. 2006

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“…No new IR absorptions of significant intensity were observed to grow in as a result. At neither this nor any earlier stage did the IR spectrum suggest the formation of a binary hydride of gallium, for example, GaH, GaH 2 , GaH 3 , or Ga 2 H 6 , [27,40] or subvalent tin, for example, SnH, SnH 2 , or SnH 3 , [20] previously characterized in varying degrees of detail. Annealing the matrix at temperatures up to about 30 K had little effect on its IR spectrum at either this or any earlier stage of its history.…”

mentioning

confidence: 84%

“…As in the experiments with Al, there was no sign of the photoreversible behavior displayed by the products M···SiH 4 [13,14] Simultaneously with the progressive depletion of the matrix in 1 b new IR absorptions belonging to a common product were observed to develop. 2 Ga 1002/906.5, [30] H 2 Ga(m-H) 2 GaH 2 1273/1202, [40] and Me 2 Ga(m-H) 2 GaMe 2 1290/ 1185 cm À1 [41] ). The IR kinship to 2 a and the circumstances of formation (from 1 b) lead us to identify the new compound as 2 b, that is, the Ga analogue of 2 a.…”

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confidence: 99%

Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH₄

Gaertner

Himmel

MacRae

et al. 2004

Chemistry A European J

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IR measurements show that co-condensation of Al or Ga atoms (M) with SnH4 in a solid Ar matrix at about 12 K results mainly in the spontaneous insertion of the metal into an Sn-H bond to form the M(II) hydride HMSnH3. Simultaneously the Ga2 dimer also reacts with SnH4, possibly to form a nido-type cluster Ga2(mu-H)4Sn, with a metal-deficient cubane-like structure. All of these products are photolabile. Irradiation with visible light causes HMSnH3 to tautomerize to the novel dihydrido-bridged species H3M(mu-H)2Sn, which decomposes in turn under broad-band UV-visible light (lambda=200-800 nm); some H3Al(mu-H)2Sn is formed even on deposition. The data collected from experiments with SnH4 and SnD4 and different reagent concentrations, together with the results of quantum chemical calculations, are used to interpret the results and elucidate the structures and bonding of the new species.

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“…Previous research carried out in our laboratories has shown that gallanes formally of the type GaH 2 X (X = GaH 4 , BH 4 , or halogen) [1,4,[5][6][7][8]15,16] resemble analogous boranes [1,17,18] in many ways in adding to amine and other donor molecules L to form (i) molecular 1:1 complexes L·GaH 2 X and (ii) 1:2 complexes with either a molecular (L 2 GaH 2 X) or an ionic formulation ([H 2 GaL 2 ] + X -). The corresponding alanes likewise form 1:1 complexes L·AlH 2 X that are molecular in nature, but 1:2 complexes are typically also molecular with a pentacoordinate metal atom.…”

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confidence: 99%

Formation and Characterization of the Cationic Gallane Derivatives [(RH₂N)₂GaH₂]Cl (R = Me or iPr) and [{(iPrH₂N)GaH₂NHiPr}₂GaH₂]Cl

et al. 2008

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The reaction of LiGaH4 with an excess of the hydrochloride of a primary amine RNH2 in ether solution yields in [(RH2N)2GaH2]Cl (R = Me, 1, or iPr, 2) additional examples of cationic gallane derivatives. The cation [(iPrH2N)2GaH2]+ reacts further with LiGaH4, also in ether solution, with H2 elimination and formation of the trigallium cationic derivative [{(iPrH2N)GaH2NHiPr}2GaH2]Cl, 3. Prolonged standing of [(iPrH2N)2GaH2]Cl in the presence of LiCl results in partial exchange of Ga–H by Ga–Cl bonds, with the isolation in low yield of crystals, 4, of [(iPrH2N)2GaH2]Cl in which about 7 % of the H atoms attached to Ga were replaced by Cl. All of the compounds 1–4 having been characterized crystallographically, the results are discussed in relation to the different reaction pathways open to [RNH3]Cl and LiMH4 (M = Al or Ga). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Gallane: synthesis, physical and chemical properties, and structure of the gaseous molecule Ga2H6 as determined by electron diffraction

Cited by 157 publications

References 1 publication

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH₄

Formation and Characterization of the Cationic Gallane Derivatives [(RH₂N)₂GaH₂]Cl (R = Me or iPr) and [{(iPrH₂N)GaH₂NHiPr}₂GaH₂]Cl

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Gallane: synthesis, physical and chemical properties, and structure of the gaseous molecule Ga2H6 as determined by electron diffraction

Cited by 157 publications

References 1 publication

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

Unusual Infrared Spectrum of Ethane Adsorbed by Gallium Oxide

Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH4

Formation and Characterization of the Cationic Gallane Derivatives [(RH2N)2GaH2]Cl (R = Me or iPr) and [{(iPrH2N)GaH2NHiPr}2GaH2]Cl

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Some Novel Binuclear Group 13 Metal Tin Hydrides Formed in Ar Matrices Following the Codeposition of the Metal Vapor with SnH₄

Formation and Characterization of the Cationic Gallane Derivatives [(RH₂N)₂GaH₂]Cl (R = Me or iPr) and [{(iPrH₂N)GaH₂NHiPr}₂GaH₂]Cl