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-Senge; Philip P. Power

doi:10.1021/ic00104a046

New Base-Free Alanes and Gallanes: Synthesis and Characterization of Monomeric Mes₂GaH (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-Senge, Philip P. Power

Research output: Contribution to journal › Article › peer-review

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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)₂C₆H₃AlH₂-(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 Kα (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 language	English (US)
Pages (from-to)	6300-6306
Number of pages	7
Journal	Inorganic Chemistry
Volume	33
Issue number	26
DOIs	https://doi.org/10.1021/ic00104a046
State	Published - Dec 1 1994
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Wehmschulte, R. J., Ellison, J. J., Ruhlandt-Senge, K., & Power, P. P. (1994). 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. Inorganic Chemistry, 33(26), 6300-6306. https://doi.org/10.1021/ic00104a046

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. / Wehmschulte, Rudolf J.; Ellison, Jeffrey J.; Ruhlandt-Senge, Karin et al.
In: Inorganic Chemistry, Vol. 33, No. 26, 01.12.1994, p. 6300-6306.

Research output: Contribution to journal › Article › peer-review

Wehmschulte, RJ, Ellison, JJ, Ruhlandt-Senge, K & Power, PP 1994, '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', Inorganic Chemistry, vol. 33, no. 26, pp. 6300-6306. https://doi.org/10.1021/ic00104a046

@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)2C6H3AlH2-(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 Kα (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-Senge and Power, {Philip P.}",

year = "1994",

month = dec,

day = "1",

doi = "10.1021/ic00104a046",

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-Senge, Karin

AU - Power, Philip P.

PY - 1994/12/1

Y1 - 1994/12/1

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)2C6H3AlH2-(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 Kα (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)2C6H3AlH2-(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 Kα (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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