Dimeric piperidino-alane and -gallane: metal hydrides with a cyclic M(µ-N)2M core (M = Al or Ga)

Tang, Christina Y.; Downs, Anthony J.; Greene, Tim M.; Parsons, Simon

doi:10.1039/b209669m

Cited by 24 publications

(9 citation statements)

References 14 publications

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“…At 1.986( 8 The [ t BuHNGaH 2 ] 2 molecules of 4, like other dimeric species of this type, contain a central, planar Ga(l-N) 2 Ga ring with symmetrical tert-butylamido bridges between the metal atoms and the t Bu substituents placed trans to each other. Averaging 1.991(3) A ˚, the Ga-N distances are not significantly different from those in 3 (where they might have been expected to be slightly longer 43 ), being at the short end of the range 1.96-2.10 A ˚observed for neutral amidogallanes containing a Ga(l-N) 2 Ga unit. 48 The corresponding distances in some related gallanes are 2.027( 4…”

Section: Methylamidogallane (3) and Tert-butylamidogallane (4)mentioning

confidence: 77%

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

et al. 2005

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Primary amine-gallane adducts, RH(2)N.GaH(3)[R = Me (1) and (t)Bu (2)], have been isolated for the first time from the reaction of [RNH(3)]Cl with LiGaH(4) in Et(2)O solution at ca. 273 K and characterised by their vibrational and (1)H NMR spectra. The structures of single crystals, grown at low temperatures and determined by X-ray diffraction, reveal pseudo-polymeric arrays of RH(2)N.GaH(3) molecules with Ga-N distances of 2.0424(18) and 2.058(5)A for 1 and 2, respectively. The adducts decompose at or near ambient temperatures with the elimination of H(2) and formation of the corresponding monoalkylamido derivative [RHNGaH(2)](n). The crystal structures of these at 150 K consist of either [MeHNGaH(2)](3) molecules with a "skew-boat" conformation for the cyclic Ga(3)N(3) skeleton (3) or [(t)BuHNGaH(2)](2) molecules with a four-membered Ga(2)N(2) core (4), with Ga-N distances averaging 1.986(8) and 1.991(3)A for 3 and 4, respectively. The crystalline solids 1, 3 and 4 feature intermolecular N-H...H-Ga interactions with H...H distances estimated to fall in the range 2.1-2.3 A. The significance of these is discussed.

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Section: Methylamidogallane (3) and Tert-butylamidogallane (4)mentioning

confidence: 77%

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

et al. 2005

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“…36 At 202.6(2) pm, the Ga-N distance falls well within the range 196-210 pm observed for other, analogous compounds in the solid state. 37 Comparable distances are 205.8 (7) 40 respectively. The Ga-N-Ga angle of 90.7(1) • , with the nearly square Ga(l-N) 2 Ga unit thus implied, is also in line with a relatively rigid unit whose shape is determined in part by cross-ring repulsive N • • • N interaction, and varies but little with substituents and environment.…”

Section: (Ii) Ged Resultsmentioning

confidence: 99%

Gas electron diffraction study of the vapour over dimethylamine–gallane leading to an improved structure for dimeric dimethylamidogallane, [Me₂NGaH₂]₂: a cautionary tale

et al. 2006

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Dimethylamine-gallane is relatively slow to decompose in a closed system and vaporises at low temperature primarily as Me2(H)N.GaH3 molecules which can be trapped in a solid Ar matrix and characterised by their IR spectrum. Under the conditions needed to secure a useful gas electron diffraction (GED) pattern, however, the vapour was found to consist of dimeric dimethylamidogallane molecules, [Me2NGaH2]2, formed from the secondary amine adduct by elimination of H2, and the most reliable structure for which has been determined. Salient structural parameters (r(hl) structure) were found to be: r(Ga-N) 202.6(2), r(Ga-H) 155.6(8), r(N-C) 148.0(3), r(C-H) 111.2(6) pm; Ga-N-Ga 90.7(1), C-N-C 109.3(5), N-C-H 109.9(10) and H-Ga-H 119.4(42) degrees.

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“…That some of the XRD experimental values for M-H differ substantially from those calculated while others are very close can be attributed mainly to the poor experimental definition of the H atom positions. 4,13,36 The bond lengths for 3 and 4 are in keeping with a general pattern. For bonds of relatively low polarity, e.g.…”

Section: Comparison Of Gas-phase Crystal and Theoretical Structures O...mentioning

confidence: 63%

Molecular structures of free quinuclidine and its adducts with metal trihydrides, MH3 (M = B, Al or Ga), studied by gas-phase electron diffraction, X-ray diffraction and quantum chemical calculations

et al. 2007

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The structure of quinuclidine, HC(CH(2)CH(2))(3)N, has been re-investigated by quantum chemical calculations and by gas-phase electron diffraction (GED). The GED data, together with published rotational constants, have been analysed using the SARACEN method to determine the most reliable structure (r(h1)) for the gaseous molecule. The structures of two adducts of quinuclidine with group 13 trihydride molecules, MH(3) (M=B, Al), have also been determined by GED and quantum chemical calculations. The effect of the coordination of these hydrides to the quinuclidine nitrogen atom has been investigated, and the structural changes and energetics of adduct formation are discussed. We also present the crystal structure of quinuclidine borane.

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Dimeric piperidino-alane and -gallane: metal hydrides with a cyclic M(µ-N)2M core (M = Al or Ga)

Cited by 24 publications

References 14 publications

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

Gas electron diffraction study of the vapour over dimethylamine–gallane leading to an improved structure for dimeric dimethylamidogallane, [Me₂NGaH₂]₂: a cautionary tale

Molecular structures of free quinuclidine and its adducts with metal trihydrides, MH3 (M = B, Al or Ga), studied by gas-phase electron diffraction, X-ray diffraction and quantum chemical calculations

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Dimeric piperidino-alane and -gallane: metal hydrides with a cyclic M(µ-N)2M core (M = Al or Ga)

Cited by 24 publications

References 14 publications

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

Synthesis and structural characterisation of primary amine adducts of gallane, RH2N·GaH3, and of their decomposition products, [RHNGaH2]n(R = Me, n= 3; R =tBu, n= 2)

Gas electron diffraction study of the vapour over dimethylamine–gallane leading to an improved structure for dimeric dimethylamidogallane, [Me2NGaH2]2: a cautionary tale

Molecular structures of free quinuclidine and its adducts with metal trihydrides, MH3 (M = B, Al or Ga), studied by gas-phase electron diffraction, X-ray diffraction and quantum chemical calculations

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Gas electron diffraction study of the vapour over dimethylamine–gallane leading to an improved structure for dimeric dimethylamidogallane, [Me₂NGaH₂]₂: a cautionary tale