Synthesis and X-ray crystallographic structures of [HGa(NMe2)2]2 and [PhGa(NHNMe2)2]2, and room-temperature conversions of [HGa(NMe2)2]2 to (HGaNH)n and (HGaNMe)n

Luo, Bing; Gladfelter, Wayne L.

doi:10.1016/j.jorganchem.2003.12.013

Cited by 18 publications

(8 citation statements)

References 17 publications

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“…Observation that the organogallium moiety remained intact under these conditions was consistent with the known robust nature of the single Ga−C bond in compounds having the formula RGaX 2 , where X is an electronegative ligand (e.g., OH), and with the low acidity of NH 3 . In analogy to the step proposed in the formation of [HGaNH] n both from [H 2 GaNH 2 ] 3 7 and [HGa(NH 2 ) 2 ] 2 , eq 4 showed loss of 2 equiv of ammonia We had no evidence to support a mechanism for this reaction, nor could we confirm that [RGaNH] monomers were the growth species in forming the oligomers.…”

Section: Discussionmentioning

confidence: 79%

Oligomeric Rods of Alkyl- and Hydridogallium Imides

et al. 2005

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Reaction of [RGa(NMe(2))(2)](2), where R = Me, Et, Bu, and Hx, with ammonia at 150 degrees C in an autoclave produced insoluble white powders formulated as oligomers of [RGaNH](n). The analogous reaction between NH(3) and MeGa[N(SiMe(3))(2)](2) at low temperature (<25 degrees C) formed an isolable intermediate, [MeGa(mu-NH(2))N(SiMe(3))(2)](2), that was characterized using single-crystal X-ray diffraction. Infrared spectroscopy and X-ray diffraction of the oligomers were consistent with a rodlike structure comprised of six-membered, [RGaNH](3) rings stacked perpendicular to the long axis of the rod. The method of synthesis, formula, and diffraction results suggested a structural similarity between the alkyl, [RGaNH](n)(), and the previously reported hydride, [HGaNH](n). The structural and electronic properties of rods having the general formula H(3)[(HXYH)(3)](n)H(3) (XY = GaN, GeC; n = 1-9) were investigated using density functional theory. Atomic electronegativity differences between the group 13/15 and 14/14 systems were found to play important roles in the geometrical structures of the two rods and also caused significant differences in the electronic structures. Energetically, it was found to be increasingly favorable to add additional cyclotrigallazane rings to the GaN rods, while for the GeC rods, there was a roughly constant energy cost associated with each additional ring. The electric dipole moments of the GaN rods increased substantially with length; in the GeC rods, charge separation occurred to a much smaller extent and had a polarization opposite to that found in GaN. In addition, increased dipole moments correlated with smaller electronic excitation energies, as predicted by time-dependent density functional theory. All of the powders exhibited luminescence in the visible spectrum at room temperature. Structure observed in the photoluminescence spectra of [HGaNH](n) and [MeGaNH](n) was interpreted as arising from rods of different length.

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Section: Discussionmentioning

confidence: 79%

Oligomeric Rods of Alkyl- and Hydridogallium Imides

et al. 2005

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“…Amide ligands have long been exploited in the stabilization of gallium hydrides, with oliomeric N-bridged structures typically predominating with simple NR 2 donors. ,− Synthetic access can be achieved via a number of routes including metathesis and protonolysis. Thus, Gladfelter and coworkers synthesized HGa(NMe 2 ) 2 ( 639 ) via the reaction of Li[NMe 2 ] with the quinuclidine adduct of dichlororogallane, quin·GaHCl 2 .…”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

“…Thus, Gladfelter and coworkers synthesized HGa(NMe 2 ) 2 ( 639 ) via the reaction of Li[NMe 2 ] with the quinuclidine adduct of dichlororogallane, quin·GaHCl 2 . Compound 639 has an archetypal dimeric structure in the solid state, [(Me 2 N)HGa(μ-NMe 2 )] 2 , featuring both bridging and terminal amide ligands and has been exploited as a source of (amorphous) polymeric [HGaNH] n or (HGaNMe) n via reactions with NH 3 or MeNH 2 , respectively . Similar metathesis processes can be used to access gallium hydride species featuring amido ligands bearing pendant amine groups, leading in some cases to the isolation of complexes of decreased nuclearity. , Thus, for example, the reaction of quin·GaHCl 2 with Li[N(CH 2 CH 2 NMe 2 ) 2 ] leads to the formation of the (monomeric) trigonal bipyramidal doubly amine-stabilized amidogallium dihydride (Me 2 NCH 2 CH 2 ) 2 GaH ( 640 ; Scheme ).…”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

“…structure in the solid state, [(Me 2 N)HGa(μ-NMe 2 )] 2 , featuring both bridging and terminal amide ligands and has been exploited as a source of (amorphous) polymeric[HGaNH] n or (HGaNMe) n via reactions with NH 3 or MeNH 2 , respectively 831. Similar metathesis processes can be used to access gallium hydride species featuring amido ligands bearing pendant amine groups, leading in some cases to the isolation of complexes of decreased nuclearity 834,835.…”

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Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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“…Generally, they were obtained by the treatment of trialkylgallium compounds [2][3][4][5][6] or stable gallium trihydride adducts [7] with different alkylhydrazines, by the reactions of dialkylgallium chlorides with lithium hydrazides [6][7][8] or by the replacement reaction between a hydrazine derivative and a gallium amide [9]. In some cases, gallium hydrazine adducts could be isolated as stable intermediates [5,6,10].…”

Section: Introductionmentioning

confidence: 99%