Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium

Penelope J. Brothers, Rudolf J. Wehmschulte, Marilyn M. Olmstead, Karin Ruhlandt, Sean R. Parkin, Philip P. Power

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Abstract

As part of a study of the possible existence of π-interactions in Al-N or Ga-N bonds, the synthesis and spectroscopic and structural characterization of several unassociated amido derivatives of aluminum and gallium are described. The compounds Mes*GaCl{N(H)Ph}·0.25 (hexane), 1, Mes*2GaN(H)Ph, 2, MesAl{N(SiMe3)2}2, 3, Mes*Ga(NHPh)2, 4, and ClGa-{N(SiMe3)2}2, 5 (Mes = 2,4,6-Me3C6H2, Mes* = 2,4,6-t-Bu3C6H2) were synthesized by simple salt elimination procedures and characterized by 1H and 13C NMR and X-ray crystallography. In addition, the X-ray crystal structures of the previously reported triamido compounds Al{N(i-Pr)2}3, 6, and Ga{N(SiMe3)2}3, 7, are described. The Al-N and Ga-N distances in 1-7 fall within the narrow limits 1.790(4)-1.809(2) and 1.829(9)-1.874(4) Å, respectively, which are within the previously known range for bonds between three-coordinate nitrogen and three-coordinate aluminum or gallium. Dynamic behavior in the 1H and 13C NMR spectra of 2 and 3 was also observed, with a barrier near 11 kcal mol-1 being estimated in both molecules. The structural and dynamic NMR data suggest that any π-interactions in the M-N bonds are rather weak and are of the order of 10 kcal mol-1. Crystal data at 130 K with Mo Kα (4, 6, 7, λ = 0.710 73 Å) or Cu Kα (1-3, 5, λ = 1.541 78 Å) radiation: (1) C25.5H38.5ClGaN, a = 9.421(2) Å, b = 14.413(2) Å, c = 18.967(3) Å, α = 87.88(2)°, β = 79.22(2)°, γ = 80.66(2)°, triclinic, space group P1, Z = 4, R = 0.083 for 3867 (I > 3σ(I)) reflections; (2) C42H64GaN, a = 9.945(2) Å, b = 11.245(2) Å, c = 17.825(2) Å, α = 87.28(2)°, β = 85.73(2)°, γ = 79.25(2)°, space group P1, Z = 2, R = 0.054 for 4155 (I > 2σ(I)) reflections; (3) C21H47AlN2Si4, a = 13.403(3) Å, b = 16.651(2) Å, c = 26.061(5) Å, β = 91.46(2)°, monoclinic, space group C2/c, Z = 8, R = 0.035 for 2992 (I > 2σ(I)) reflections; (4) C30H30GaN2, a = 20.346(4) Å, b = 11.696(3) Å, c = 13.565(3) Å, β = 123.17(2)°, monoclinic, space group C2/c, Z = 4, R = 0.066 for 1707 (I > 3σ(I)) reflections; (5) C12H36ClGaN2Si4, a = 11.657(3) Å, b = 12.677(2) Å, c = 15.831(3) Å, orthorhombic, space group P212121, Z = 4, R = 0.040 for 2577 (I > 3σ(I)) reflections; (6) C18H42AlN3, a = 7.803(6) Å, b = 16.590(12) Å, c = 17.397(14) Å, α = 102.68(5), β = 90.67(5)°, γ = 96.67(5)°, triclinic, space group P1, Z = 4, R = 0.071 for 4311 (I > 2σ(I)) data; (7) C18H54GaN3Si6, a = 16.008(3) Å, c = 8.444(2) Å, trigonal, space group P31c, Z = 2, R = 0.059 for 718 (I > 3σ(I)) reflections.

Original languageEnglish (US)
Pages (from-to)2792-2799
Number of pages8
JournalOrganometallics
Volume13
Issue number7
StatePublished - 1994
Externally publishedYes

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Gallium
Aluminum
gallium
Derivatives
aluminum
synthesis
Nuclear magnetic resonance
nuclear magnetic resonance
X ray crystallography
Hexanes
Nitrogen
crystallography
Salts
Crystal structure
elimination
x rays
Radiation
X rays
interactions
Crystals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Brothers, P. J., Wehmschulte, R. J., Olmstead, M. M., Ruhlandt, K., Parkin, S. R., & Power, P. P. (1994). Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium. Organometallics, 13(7), 2792-2799.

Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium. / Brothers, Penelope J.; Wehmschulte, Rudolf J.; Olmstead, Marilyn M.; Ruhlandt, Karin; Parkin, Sean R.; Power, Philip P.

In: Organometallics, Vol. 13, No. 7, 1994, p. 2792-2799.

Research output: Contribution to journalArticle

Brothers, PJ, Wehmschulte, RJ, Olmstead, MM, Ruhlandt, K, Parkin, SR & Power, PP 1994, 'Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium', Organometallics, vol. 13, no. 7, pp. 2792-2799.
Brothers, Penelope J. ; Wehmschulte, Rudolf J. ; Olmstead, Marilyn M. ; Ruhlandt, Karin ; Parkin, Sean R. ; Power, Philip P. / Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium. In: Organometallics. 1994 ; Vol. 13, No. 7. pp. 2792-2799.
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title = "Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium",
abstract = "As part of a study of the possible existence of π-interactions in Al-N or Ga-N bonds, the synthesis and spectroscopic and structural characterization of several unassociated amido derivatives of aluminum and gallium are described. The compounds Mes*GaCl{N(H)Ph}·0.25 (hexane), 1, Mes*2GaN(H)Ph, 2, MesAl{N(SiMe3)2}2, 3, Mes*Ga(NHPh)2, 4, and ClGa-{N(SiMe3)2}2, 5 (Mes = 2,4,6-Me3C6H2, Mes* = 2,4,6-t-Bu3C6H2) were synthesized by simple salt elimination procedures and characterized by 1H and 13C NMR and X-ray crystallography. In addition, the X-ray crystal structures of the previously reported triamido compounds Al{N(i-Pr)2}3, 6, and Ga{N(SiMe3)2}3, 7, are described. The Al-N and Ga-N distances in 1-7 fall within the narrow limits 1.790(4)-1.809(2) and 1.829(9)-1.874(4) {\AA}, respectively, which are within the previously known range for bonds between three-coordinate nitrogen and three-coordinate aluminum or gallium. Dynamic behavior in the 1H and 13C NMR spectra of 2 and 3 was also observed, with a barrier near 11 kcal mol-1 being estimated in both molecules. The structural and dynamic NMR data suggest that any π-interactions in the M-N bonds are rather weak and are of the order of 10 kcal mol-1. Crystal data at 130 K with Mo Kα (4, 6, 7, λ = 0.710 73 {\AA}) or Cu Kα (1-3, 5, λ = 1.541 78 {\AA}) radiation: (1) C25.5H38.5ClGaN, a = 9.421(2) {\AA}, b = 14.413(2) {\AA}, c = 18.967(3) {\AA}, α = 87.88(2)°, β = 79.22(2)°, γ = 80.66(2)°, triclinic, space group P1, Z = 4, R = 0.083 for 3867 (I > 3σ(I)) reflections; (2) C42H64GaN, a = 9.945(2) {\AA}, b = 11.245(2) {\AA}, c = 17.825(2) {\AA}, α = 87.28(2)°, β = 85.73(2)°, γ = 79.25(2)°, space group P1, Z = 2, R = 0.054 for 4155 (I > 2σ(I)) reflections; (3) C21H47AlN2Si4, a = 13.403(3) {\AA}, b = 16.651(2) {\AA}, c = 26.061(5) {\AA}, β = 91.46(2)°, monoclinic, space group C2/c, Z = 8, R = 0.035 for 2992 (I > 2σ(I)) reflections; (4) C30H30GaN2, a = 20.346(4) {\AA}, b = 11.696(3) {\AA}, c = 13.565(3) {\AA}, β = 123.17(2)°, monoclinic, space group C2/c, Z = 4, R = 0.066 for 1707 (I > 3σ(I)) reflections; (5) C12H36ClGaN2Si4, a = 11.657(3) {\AA}, b = 12.677(2) {\AA}, c = 15.831(3) {\AA}, orthorhombic, space group P212121, Z = 4, R = 0.040 for 2577 (I > 3σ(I)) reflections; (6) C18H42AlN3, a = 7.803(6) {\AA}, b = 16.590(12) {\AA}, c = 17.397(14) {\AA}, α = 102.68(5), β = 90.67(5)°, γ = 96.67(5)°, triclinic, space group P1, Z = 4, R = 0.071 for 4311 (I > 2σ(I)) data; (7) C18H54GaN3Si6, a = 16.008(3) {\AA}, c = 8.444(2) {\AA}, trigonal, space group P31c, Z = 2, R = 0.059 for 718 (I > 3σ(I)) reflections.",
author = "Brothers, {Penelope J.} and Wehmschulte, {Rudolf J.} and Olmstead, {Marilyn M.} and Karin Ruhlandt and Parkin, {Sean R.} and Power, {Philip P.}",
year = "1994",
language = "English (US)",
volume = "13",
pages = "2792--2799",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "7",

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TY - JOUR

T1 - Synthesis, structure, and spectroscopic characterization of unassociated mono-, di-, and triamido derivatives of aluminum and gallium

AU - Brothers, Penelope J.

AU - Wehmschulte, Rudolf J.

AU - Olmstead, Marilyn M.

AU - Ruhlandt, Karin

AU - Parkin, Sean R.

AU - Power, Philip P.

PY - 1994

Y1 - 1994

N2 - As part of a study of the possible existence of π-interactions in Al-N or Ga-N bonds, the synthesis and spectroscopic and structural characterization of several unassociated amido derivatives of aluminum and gallium are described. The compounds Mes*GaCl{N(H)Ph}·0.25 (hexane), 1, Mes*2GaN(H)Ph, 2, MesAl{N(SiMe3)2}2, 3, Mes*Ga(NHPh)2, 4, and ClGa-{N(SiMe3)2}2, 5 (Mes = 2,4,6-Me3C6H2, Mes* = 2,4,6-t-Bu3C6H2) were synthesized by simple salt elimination procedures and characterized by 1H and 13C NMR and X-ray crystallography. In addition, the X-ray crystal structures of the previously reported triamido compounds Al{N(i-Pr)2}3, 6, and Ga{N(SiMe3)2}3, 7, are described. The Al-N and Ga-N distances in 1-7 fall within the narrow limits 1.790(4)-1.809(2) and 1.829(9)-1.874(4) Å, respectively, which are within the previously known range for bonds between three-coordinate nitrogen and three-coordinate aluminum or gallium. Dynamic behavior in the 1H and 13C NMR spectra of 2 and 3 was also observed, with a barrier near 11 kcal mol-1 being estimated in both molecules. The structural and dynamic NMR data suggest that any π-interactions in the M-N bonds are rather weak and are of the order of 10 kcal mol-1. Crystal data at 130 K with Mo Kα (4, 6, 7, λ = 0.710 73 Å) or Cu Kα (1-3, 5, λ = 1.541 78 Å) radiation: (1) C25.5H38.5ClGaN, a = 9.421(2) Å, b = 14.413(2) Å, c = 18.967(3) Å, α = 87.88(2)°, β = 79.22(2)°, γ = 80.66(2)°, triclinic, space group P1, Z = 4, R = 0.083 for 3867 (I > 3σ(I)) reflections; (2) C42H64GaN, a = 9.945(2) Å, b = 11.245(2) Å, c = 17.825(2) Å, α = 87.28(2)°, β = 85.73(2)°, γ = 79.25(2)°, space group P1, Z = 2, R = 0.054 for 4155 (I > 2σ(I)) reflections; (3) C21H47AlN2Si4, a = 13.403(3) Å, b = 16.651(2) Å, c = 26.061(5) Å, β = 91.46(2)°, monoclinic, space group C2/c, Z = 8, R = 0.035 for 2992 (I > 2σ(I)) reflections; (4) C30H30GaN2, a = 20.346(4) Å, b = 11.696(3) Å, c = 13.565(3) Å, β = 123.17(2)°, monoclinic, space group C2/c, Z = 4, R = 0.066 for 1707 (I > 3σ(I)) reflections; (5) C12H36ClGaN2Si4, a = 11.657(3) Å, b = 12.677(2) Å, c = 15.831(3) Å, orthorhombic, space group P212121, Z = 4, R = 0.040 for 2577 (I > 3σ(I)) reflections; (6) C18H42AlN3, a = 7.803(6) Å, b = 16.590(12) Å, c = 17.397(14) Å, α = 102.68(5), β = 90.67(5)°, γ = 96.67(5)°, triclinic, space group P1, Z = 4, R = 0.071 for 4311 (I > 2σ(I)) data; (7) C18H54GaN3Si6, a = 16.008(3) Å, c = 8.444(2) Å, trigonal, space group P31c, Z = 2, R = 0.059 for 718 (I > 3σ(I)) reflections.

AB - As part of a study of the possible existence of π-interactions in Al-N or Ga-N bonds, the synthesis and spectroscopic and structural characterization of several unassociated amido derivatives of aluminum and gallium are described. The compounds Mes*GaCl{N(H)Ph}·0.25 (hexane), 1, Mes*2GaN(H)Ph, 2, MesAl{N(SiMe3)2}2, 3, Mes*Ga(NHPh)2, 4, and ClGa-{N(SiMe3)2}2, 5 (Mes = 2,4,6-Me3C6H2, Mes* = 2,4,6-t-Bu3C6H2) were synthesized by simple salt elimination procedures and characterized by 1H and 13C NMR and X-ray crystallography. In addition, the X-ray crystal structures of the previously reported triamido compounds Al{N(i-Pr)2}3, 6, and Ga{N(SiMe3)2}3, 7, are described. The Al-N and Ga-N distances in 1-7 fall within the narrow limits 1.790(4)-1.809(2) and 1.829(9)-1.874(4) Å, respectively, which are within the previously known range for bonds between three-coordinate nitrogen and three-coordinate aluminum or gallium. Dynamic behavior in the 1H and 13C NMR spectra of 2 and 3 was also observed, with a barrier near 11 kcal mol-1 being estimated in both molecules. The structural and dynamic NMR data suggest that any π-interactions in the M-N bonds are rather weak and are of the order of 10 kcal mol-1. Crystal data at 130 K with Mo Kα (4, 6, 7, λ = 0.710 73 Å) or Cu Kα (1-3, 5, λ = 1.541 78 Å) radiation: (1) C25.5H38.5ClGaN, a = 9.421(2) Å, b = 14.413(2) Å, c = 18.967(3) Å, α = 87.88(2)°, β = 79.22(2)°, γ = 80.66(2)°, triclinic, space group P1, Z = 4, R = 0.083 for 3867 (I > 3σ(I)) reflections; (2) C42H64GaN, a = 9.945(2) Å, b = 11.245(2) Å, c = 17.825(2) Å, α = 87.28(2)°, β = 85.73(2)°, γ = 79.25(2)°, space group P1, Z = 2, R = 0.054 for 4155 (I > 2σ(I)) reflections; (3) C21H47AlN2Si4, a = 13.403(3) Å, b = 16.651(2) Å, c = 26.061(5) Å, β = 91.46(2)°, monoclinic, space group C2/c, Z = 8, R = 0.035 for 2992 (I > 2σ(I)) reflections; (4) C30H30GaN2, a = 20.346(4) Å, b = 11.696(3) Å, c = 13.565(3) Å, β = 123.17(2)°, monoclinic, space group C2/c, Z = 4, R = 0.066 for 1707 (I > 3σ(I)) reflections; (5) C12H36ClGaN2Si4, a = 11.657(3) Å, b = 12.677(2) Å, c = 15.831(3) Å, orthorhombic, space group P212121, Z = 4, R = 0.040 for 2577 (I > 3σ(I)) reflections; (6) C18H42AlN3, a = 7.803(6) Å, b = 16.590(12) Å, c = 17.397(14) Å, α = 102.68(5), β = 90.67(5)°, γ = 96.67(5)°, triclinic, space group P1, Z = 4, R = 0.071 for 4311 (I > 2σ(I)) data; (7) C18H54GaN3Si6, a = 16.008(3) Å, c = 8.444(2) Å, trigonal, space group P31c, Z = 2, R = 0.059 for 718 (I > 3σ(I)) reflections.

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