New base-free alanes and gallanes: Synthesis and characterization of monomeric Mes*2GaH (Mes* = 2,4,6-t-Bu3C6H2), Dimeric (Trip2MH)2 (Trip = 2,4,6-i-Pr3C6H2; M = Al, Ga), and related sterically crowded arylaluminum species

Rudolf J. Wehmschulte, Jeffrey J. Ellison, Karin Ruhlandt, Philip P. Power

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Abstract

The synthesis and characterization of several hydrido derivatives of aluminum and gallium which have bulky aryl substituents are described. The neutral derivatives Mes*2GaH (1), (Trip2GaH)2 (2), and (Trip2AlH)2 (3) (Mes* = 2,4,6-t-Bu3C6H2; Trip = 2,4,6-i-Pr3C6H2) were synthesized by the reaction of t-BuLi with the corresponding halide derivatives. The X-ray crystal structures of 1-3 were also determined, and these showed that 1 was monomeric whereas 2 and 3 were dimeric with hydrogen bridging. VT NMR data for 2 indicated that it underwent significant dissociation in solution whereas 3 remains almost completely associated in toluene-d8 at room temperature. The synthesis and structural characterization of the aluminate species [TriphAlH3Li(Et2O)1.5]2 (4) (Triph = 2,4,6-Ph3C6H2) and [Mes*AlH3Li(THF)2]2 (5) and the neutral adduct [2,6-(4-t-BuC6H4)2C6H 3AlH2-(NMe3)] (6) are also reported. These compounds are of importance in the synthesis of neutral uncomplexed hydrido derivatives. Crystal data at 130 K with Cu Ka (1-3, λ = 1.541 78 Å) or Mo Kα (4-6, λ = 0.710 73 Å) radiation: 1, C36H59Ga, a = 9.919(2) Å, b = 29.443(3) Å, c = 11.388(2) Å, β = 94.72(2)°, monoclinic, space group P21/c, Z = 4, R = 0.044 for 3694 (I > 2σ(I)) data; 2, C60H94Ga2, a = 14.994(7) Å, b = 10.263(4) Å, c = 37.375(13) Å, β = 95.56(3)°, monoclinic, space group P21/c, Z = 4, R = 0.068 for 6112 (I > 2σ(I)) data; 3·PhMe, C67H102Al2, a = 21.254(4) Å, b = 23.318(3) Å, c = 25.197(3) Å, orthorhombic, space group Ibca, Z = 8, R = 0.069 for 3244 (I > 2σ(I)) data; 4, C60H70Al2Li2O3, a = 21.960(9) Å, b = 15.835(7) Å, c = 16.363(5) Å, β = 102.30(3)°, monoclinic, space group C2/c, Z = 4, R = 0.073 for 4011 (I > 3σ(I)) data; 5, C52H96Al2-Li2O4, a = 13.882(4) Å, b = 19.038(5) Å, c = 10.534(3) Å, β = 101.02(2)°, monoclinic, space group P21/c, Z = 2, R = 0.084 for 2703 (I > 2σ(I)) data; 6, C29H40AlN, a = 6.225(2) Å, b = 17.016(2) Å, c = 12.668(3) Å, β = 102.57(2)°, monoclinic, space group P21, Z = 2, R = 0.035 for 2883 (I > 2σ(I)) data.

Original languageEnglish (US)
Pages (from-to)6300-6306
Number of pages7
JournalInorganic Chemistry
Volume33
Issue number26
StatePublished - 1994
Externally publishedYes

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Derivatives
synthesis
Gallium
Toluene
Aluminum
Hydrogen
Crystal structure
Nuclear magnetic resonance
Radiation
X rays
Crystals
adducts
halides
gallium
toluene
dissociation
aluminum
nuclear magnetic resonance
crystal structure
room temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{c052a5b375634514936646a930dc40dc,
title = "New base-free alanes and gallanes: Synthesis and characterization of monomeric Mes*2GaH (Mes* = 2,4,6-t-Bu3C6H2), Dimeric (Trip2MH)2 (Trip = 2,4,6-i-Pr3C6H2; M = Al, Ga), and related sterically crowded arylaluminum species",
abstract = "The synthesis and characterization of several hydrido derivatives of aluminum and gallium which have bulky aryl substituents are described. The neutral derivatives Mes*2GaH (1), (Trip2GaH)2 (2), and (Trip2AlH)2 (3) (Mes* = 2,4,6-t-Bu3C6H2; Trip = 2,4,6-i-Pr3C6H2) were synthesized by the reaction of t-BuLi with the corresponding halide derivatives. The X-ray crystal structures of 1-3 were also determined, and these showed that 1 was monomeric whereas 2 and 3 were dimeric with hydrogen bridging. VT NMR data for 2 indicated that it underwent significant dissociation in solution whereas 3 remains almost completely associated in toluene-d8 at room temperature. The synthesis and structural characterization of the aluminate species [TriphAlH3Li(Et2O)1.5]2 (4) (Triph = 2,4,6-Ph3C6H2) and [Mes*AlH3Li(THF)2]2 (5) and the neutral adduct [2,6-(4-t-BuC6H4)2C6H 3AlH2-(NMe3)] (6) are also reported. These compounds are of importance in the synthesis of neutral uncomplexed hydrido derivatives. Crystal data at 130 K with Cu Ka (1-3, λ = 1.541 78 {\AA}) or Mo Kα (4-6, λ = 0.710 73 {\AA}) radiation: 1, C36H59Ga, a = 9.919(2) {\AA}, b = 29.443(3) {\AA}, c = 11.388(2) {\AA}, β = 94.72(2)°, monoclinic, space group P21/c, Z = 4, R = 0.044 for 3694 (I > 2σ(I)) data; 2, C60H94Ga2, a = 14.994(7) {\AA}, b = 10.263(4) {\AA}, c = 37.375(13) {\AA}, β = 95.56(3)°, monoclinic, space group P21/c, Z = 4, R = 0.068 for 6112 (I > 2σ(I)) data; 3·PhMe, C67H102Al2, a = 21.254(4) {\AA}, b = 23.318(3) {\AA}, c = 25.197(3) {\AA}, orthorhombic, space group Ibca, Z = 8, R = 0.069 for 3244 (I > 2σ(I)) data; 4, C60H70Al2Li2O3, a = 21.960(9) {\AA}, b = 15.835(7) {\AA}, c = 16.363(5) {\AA}, β = 102.30(3)°, monoclinic, space group C2/c, Z = 4, R = 0.073 for 4011 (I > 3σ(I)) data; 5, C52H96Al2-Li2O4, a = 13.882(4) {\AA}, b = 19.038(5) {\AA}, c = 10.534(3) {\AA}, β = 101.02(2)°, monoclinic, space group P21/c, Z = 2, R = 0.084 for 2703 (I > 2σ(I)) data; 6, C29H40AlN, a = 6.225(2) {\AA}, b = 17.016(2) {\AA}, c = 12.668(3) {\AA}, β = 102.57(2)°, monoclinic, space group P21, Z = 2, R = 0.035 for 2883 (I > 2σ(I)) data.",
author = "Wehmschulte, {Rudolf J.} and Ellison, {Jeffrey J.} and Karin Ruhlandt and Power, {Philip P.}",
year = "1994",
language = "English (US)",
volume = "33",
pages = "6300--6306",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "26",

}

TY - JOUR

T1 - New base-free alanes and gallanes

T2 - Synthesis and characterization of monomeric Mes*2GaH (Mes* = 2,4,6-t-Bu3C6H2), Dimeric (Trip2MH)2 (Trip = 2,4,6-i-Pr3C6H2; M = Al, Ga), and related sterically crowded arylaluminum species

AU - Wehmschulte, Rudolf J.

AU - Ellison, Jeffrey J.

AU - Ruhlandt, Karin

AU - Power, Philip P.

PY - 1994

Y1 - 1994

N2 - The synthesis and characterization of several hydrido derivatives of aluminum and gallium which have bulky aryl substituents are described. The neutral derivatives Mes*2GaH (1), (Trip2GaH)2 (2), and (Trip2AlH)2 (3) (Mes* = 2,4,6-t-Bu3C6H2; Trip = 2,4,6-i-Pr3C6H2) were synthesized by the reaction of t-BuLi with the corresponding halide derivatives. The X-ray crystal structures of 1-3 were also determined, and these showed that 1 was monomeric whereas 2 and 3 were dimeric with hydrogen bridging. VT NMR data for 2 indicated that it underwent significant dissociation in solution whereas 3 remains almost completely associated in toluene-d8 at room temperature. The synthesis and structural characterization of the aluminate species [TriphAlH3Li(Et2O)1.5]2 (4) (Triph = 2,4,6-Ph3C6H2) and [Mes*AlH3Li(THF)2]2 (5) and the neutral adduct [2,6-(4-t-BuC6H4)2C6H 3AlH2-(NMe3)] (6) are also reported. These compounds are of importance in the synthesis of neutral uncomplexed hydrido derivatives. Crystal data at 130 K with Cu Ka (1-3, λ = 1.541 78 Å) or Mo Kα (4-6, λ = 0.710 73 Å) radiation: 1, C36H59Ga, a = 9.919(2) Å, b = 29.443(3) Å, c = 11.388(2) Å, β = 94.72(2)°, monoclinic, space group P21/c, Z = 4, R = 0.044 for 3694 (I > 2σ(I)) data; 2, C60H94Ga2, a = 14.994(7) Å, b = 10.263(4) Å, c = 37.375(13) Å, β = 95.56(3)°, monoclinic, space group P21/c, Z = 4, R = 0.068 for 6112 (I > 2σ(I)) data; 3·PhMe, C67H102Al2, a = 21.254(4) Å, b = 23.318(3) Å, c = 25.197(3) Å, orthorhombic, space group Ibca, Z = 8, R = 0.069 for 3244 (I > 2σ(I)) data; 4, C60H70Al2Li2O3, a = 21.960(9) Å, b = 15.835(7) Å, c = 16.363(5) Å, β = 102.30(3)°, monoclinic, space group C2/c, Z = 4, R = 0.073 for 4011 (I > 3σ(I)) data; 5, C52H96Al2-Li2O4, a = 13.882(4) Å, b = 19.038(5) Å, c = 10.534(3) Å, β = 101.02(2)°, monoclinic, space group P21/c, Z = 2, R = 0.084 for 2703 (I > 2σ(I)) data; 6, C29H40AlN, a = 6.225(2) Å, b = 17.016(2) Å, c = 12.668(3) Å, β = 102.57(2)°, monoclinic, space group P21, Z = 2, R = 0.035 for 2883 (I > 2σ(I)) data.

AB - The synthesis and characterization of several hydrido derivatives of aluminum and gallium which have bulky aryl substituents are described. The neutral derivatives Mes*2GaH (1), (Trip2GaH)2 (2), and (Trip2AlH)2 (3) (Mes* = 2,4,6-t-Bu3C6H2; Trip = 2,4,6-i-Pr3C6H2) were synthesized by the reaction of t-BuLi with the corresponding halide derivatives. The X-ray crystal structures of 1-3 were also determined, and these showed that 1 was monomeric whereas 2 and 3 were dimeric with hydrogen bridging. VT NMR data for 2 indicated that it underwent significant dissociation in solution whereas 3 remains almost completely associated in toluene-d8 at room temperature. The synthesis and structural characterization of the aluminate species [TriphAlH3Li(Et2O)1.5]2 (4) (Triph = 2,4,6-Ph3C6H2) and [Mes*AlH3Li(THF)2]2 (5) and the neutral adduct [2,6-(4-t-BuC6H4)2C6H 3AlH2-(NMe3)] (6) are also reported. These compounds are of importance in the synthesis of neutral uncomplexed hydrido derivatives. Crystal data at 130 K with Cu Ka (1-3, λ = 1.541 78 Å) or Mo Kα (4-6, λ = 0.710 73 Å) radiation: 1, C36H59Ga, a = 9.919(2) Å, b = 29.443(3) Å, c = 11.388(2) Å, β = 94.72(2)°, monoclinic, space group P21/c, Z = 4, R = 0.044 for 3694 (I > 2σ(I)) data; 2, C60H94Ga2, a = 14.994(7) Å, b = 10.263(4) Å, c = 37.375(13) Å, β = 95.56(3)°, monoclinic, space group P21/c, Z = 4, R = 0.068 for 6112 (I > 2σ(I)) data; 3·PhMe, C67H102Al2, a = 21.254(4) Å, b = 23.318(3) Å, c = 25.197(3) Å, orthorhombic, space group Ibca, Z = 8, R = 0.069 for 3244 (I > 2σ(I)) data; 4, C60H70Al2Li2O3, a = 21.960(9) Å, b = 15.835(7) Å, c = 16.363(5) Å, β = 102.30(3)°, monoclinic, space group C2/c, Z = 4, R = 0.073 for 4011 (I > 3σ(I)) data; 5, C52H96Al2-Li2O4, a = 13.882(4) Å, b = 19.038(5) Å, c = 10.534(3) Å, β = 101.02(2)°, monoclinic, space group P21/c, Z = 2, R = 0.084 for 2703 (I > 2σ(I)) data; 6, C29H40AlN, a = 6.225(2) Å, b = 17.016(2) Å, c = 12.668(3) Å, β = 102.57(2)°, monoclinic, space group P21, Z = 2, R = 0.035 for 2883 (I > 2σ(I)) data.

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