Synthesis and characterization of the monomeric aluminum monoamides (t-Bu)2AlN(R)R′ (R and R′ = bulky aryl, alkyl, or silyl groups)

Mark A. Petrie, Karin Ruhlandt, Philip P. Power

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Abstract

The synthesis and characterization of the compounds (t-Bu)2AlNR2 (R = Mes, 1, and SiPh3, 2) and (t-Bu)2AlN(R′)SiPh3 (R′ = 2,6-i-Pr2C6H3 (Dipp), 3, and 1-adamantyl (1-Ad), 4) are described. They were characterized by X-ray crystallography and 1H NMR and IR spectroscopy. In the crystal phase, the structures of 1-4 are monomeric with essentially trigonal planar coordinations at aluminum and nitrogen and Al-N bond lengths that range from 1.82 to 1.89 Å. The variation in the Al-N bond lengths are a consequence of the steric interactions between the large groups at aluminum and nitrogen, different change separations across the Al-N bond, and, in some instances, weak Al-N π-bonding. The structural data together with VT 1H NMR studies of these and related compounds indicate that a decrease in the size of these groups affords considerably shorter Al-N distances and, in some cases, barriers to rotation around the Al-N bond that have a maximum value of ca. 9-10 kcal mol-1. The synthesis and characterization of [(t-Bu)2Al{N(H)CPh3}2(Li)], 5, are also described. Crystal data with Mo Kα (λ = 0.710 69 Å) at 130 K: 1, C26H40AlN, a = 9.965(3) Å, b = 13.746(5) Å, c = 17.700(6) Å, orthorhombic, space group Pca21, Z = 4, R = 0.069; 2, C44H48AlNSi2, a = 12.623(4) Å, b = 16.880(3) Å, c = 18.600(2) Å, α = 93.45(1)°, β = 100.25(2)°, γ = 99.46(2)°, triclinic, space group P1, Z = 4, R = 0.051; 3, C38H50AlNSi, a = 10.413(4) Å, b = 10.585(6) Å, c = 18.281(6) Å, α = 97.75(4)°, β = 96.41(3)°, γ = 118.97(2)°, triclinic, space group P1, Z = 2, R = 0.050; 4, C36H48AlNSi, a= 10.372(3) Å, b= 17.957(8) Å, c = 19.184(8) Å, α = 113.87(3)°, β = 99.23(3)°, γ = 96.71(3)°, triclinic, space group P1, Z = 4, R = 0.045; 5, C46H50AlLiN2, a = 37.78(2) Å, b = 10.635(4) Å, c = 19.237(7) Å, β = 98.19(3)°, monoclinic, space group C2/c, Z = 8, R = 0.056.

Original languageEnglish (US)
Pages (from-to)1135-1141
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number7
StatePublished - 1993
Externally publishedYes

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Bond length
Aluminum
Nitrogen
aluminum
Crystals
X ray crystallography
synthesis
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Nuclear magnetic resonance
nitrogen
nuclear magnetic resonance
crystallography
crystals
spectroscopy
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis and characterization of the monomeric aluminum monoamides (t-Bu)2AlN(R)R′ (R and R′ = bulky aryl, alkyl, or silyl groups). / Petrie, Mark A.; Ruhlandt, Karin; Power, Philip P.

In: Inorganic Chemistry, Vol. 32, No. 7, 1993, p. 1135-1141.

Research output: Contribution to journalArticle

@article{0eb1e3d611dc4a218ae43f5faf7004b9,
title = "Synthesis and characterization of the monomeric aluminum monoamides (t-Bu)2AlN(R)R′ (R and R′ = bulky aryl, alkyl, or silyl groups)",
abstract = "The synthesis and characterization of the compounds (t-Bu)2AlNR2 (R = Mes, 1, and SiPh3, 2) and (t-Bu)2AlN(R′)SiPh3 (R′ = 2,6-i-Pr2C6H3 (Dipp), 3, and 1-adamantyl (1-Ad), 4) are described. They were characterized by X-ray crystallography and 1H NMR and IR spectroscopy. In the crystal phase, the structures of 1-4 are monomeric with essentially trigonal planar coordinations at aluminum and nitrogen and Al-N bond lengths that range from 1.82 to 1.89 {\AA}. The variation in the Al-N bond lengths are a consequence of the steric interactions between the large groups at aluminum and nitrogen, different change separations across the Al-N bond, and, in some instances, weak Al-N π-bonding. The structural data together with VT 1H NMR studies of these and related compounds indicate that a decrease in the size of these groups affords considerably shorter Al-N distances and, in some cases, barriers to rotation around the Al-N bond that have a maximum value of ca. 9-10 kcal mol-1. The synthesis and characterization of [(t-Bu)2Al{N(H)CPh3}2(Li)], 5, are also described. Crystal data with Mo Kα (λ = 0.710 69 {\AA}) at 130 K: 1, C26H40AlN, a = 9.965(3) {\AA}, b = 13.746(5) {\AA}, c = 17.700(6) {\AA}, orthorhombic, space group Pca21, Z = 4, R = 0.069; 2, C44H48AlNSi2, a = 12.623(4) {\AA}, b = 16.880(3) {\AA}, c = 18.600(2) {\AA}, α = 93.45(1)°, β = 100.25(2)°, γ = 99.46(2)°, triclinic, space group P1, Z = 4, R = 0.051; 3, C38H50AlNSi, a = 10.413(4) {\AA}, b = 10.585(6) {\AA}, c = 18.281(6) {\AA}, α = 97.75(4)°, β = 96.41(3)°, γ = 118.97(2)°, triclinic, space group P1, Z = 2, R = 0.050; 4, C36H48AlNSi, a= 10.372(3) {\AA}, b= 17.957(8) {\AA}, c = 19.184(8) {\AA}, α = 113.87(3)°, β = 99.23(3)°, γ = 96.71(3)°, triclinic, space group P1, Z = 4, R = 0.045; 5, C46H50AlLiN2, a = 37.78(2) {\AA}, b = 10.635(4) {\AA}, c = 19.237(7) {\AA}, β = 98.19(3)°, monoclinic, space group C2/c, Z = 8, R = 0.056.",
author = "Petrie, {Mark A.} and Karin Ruhlandt and Power, {Philip P.}",
year = "1993",
language = "English (US)",
volume = "32",
pages = "1135--1141",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "7",

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TY - JOUR

T1 - Synthesis and characterization of the monomeric aluminum monoamides (t-Bu)2AlN(R)R′ (R and R′ = bulky aryl, alkyl, or silyl groups)

AU - Petrie, Mark A.

AU - Ruhlandt, Karin

AU - Power, Philip P.

PY - 1993

Y1 - 1993

N2 - The synthesis and characterization of the compounds (t-Bu)2AlNR2 (R = Mes, 1, and SiPh3, 2) and (t-Bu)2AlN(R′)SiPh3 (R′ = 2,6-i-Pr2C6H3 (Dipp), 3, and 1-adamantyl (1-Ad), 4) are described. They were characterized by X-ray crystallography and 1H NMR and IR spectroscopy. In the crystal phase, the structures of 1-4 are monomeric with essentially trigonal planar coordinations at aluminum and nitrogen and Al-N bond lengths that range from 1.82 to 1.89 Å. The variation in the Al-N bond lengths are a consequence of the steric interactions between the large groups at aluminum and nitrogen, different change separations across the Al-N bond, and, in some instances, weak Al-N π-bonding. The structural data together with VT 1H NMR studies of these and related compounds indicate that a decrease in the size of these groups affords considerably shorter Al-N distances and, in some cases, barriers to rotation around the Al-N bond that have a maximum value of ca. 9-10 kcal mol-1. The synthesis and characterization of [(t-Bu)2Al{N(H)CPh3}2(Li)], 5, are also described. Crystal data with Mo Kα (λ = 0.710 69 Å) at 130 K: 1, C26H40AlN, a = 9.965(3) Å, b = 13.746(5) Å, c = 17.700(6) Å, orthorhombic, space group Pca21, Z = 4, R = 0.069; 2, C44H48AlNSi2, a = 12.623(4) Å, b = 16.880(3) Å, c = 18.600(2) Å, α = 93.45(1)°, β = 100.25(2)°, γ = 99.46(2)°, triclinic, space group P1, Z = 4, R = 0.051; 3, C38H50AlNSi, a = 10.413(4) Å, b = 10.585(6) Å, c = 18.281(6) Å, α = 97.75(4)°, β = 96.41(3)°, γ = 118.97(2)°, triclinic, space group P1, Z = 2, R = 0.050; 4, C36H48AlNSi, a= 10.372(3) Å, b= 17.957(8) Å, c = 19.184(8) Å, α = 113.87(3)°, β = 99.23(3)°, γ = 96.71(3)°, triclinic, space group P1, Z = 4, R = 0.045; 5, C46H50AlLiN2, a = 37.78(2) Å, b = 10.635(4) Å, c = 19.237(7) Å, β = 98.19(3)°, monoclinic, space group C2/c, Z = 8, R = 0.056.

AB - The synthesis and characterization of the compounds (t-Bu)2AlNR2 (R = Mes, 1, and SiPh3, 2) and (t-Bu)2AlN(R′)SiPh3 (R′ = 2,6-i-Pr2C6H3 (Dipp), 3, and 1-adamantyl (1-Ad), 4) are described. They were characterized by X-ray crystallography and 1H NMR and IR spectroscopy. In the crystal phase, the structures of 1-4 are monomeric with essentially trigonal planar coordinations at aluminum and nitrogen and Al-N bond lengths that range from 1.82 to 1.89 Å. The variation in the Al-N bond lengths are a consequence of the steric interactions between the large groups at aluminum and nitrogen, different change separations across the Al-N bond, and, in some instances, weak Al-N π-bonding. The structural data together with VT 1H NMR studies of these and related compounds indicate that a decrease in the size of these groups affords considerably shorter Al-N distances and, in some cases, barriers to rotation around the Al-N bond that have a maximum value of ca. 9-10 kcal mol-1. The synthesis and characterization of [(t-Bu)2Al{N(H)CPh3}2(Li)], 5, are also described. Crystal data with Mo Kα (λ = 0.710 69 Å) at 130 K: 1, C26H40AlN, a = 9.965(3) Å, b = 13.746(5) Å, c = 17.700(6) Å, orthorhombic, space group Pca21, Z = 4, R = 0.069; 2, C44H48AlNSi2, a = 12.623(4) Å, b = 16.880(3) Å, c = 18.600(2) Å, α = 93.45(1)°, β = 100.25(2)°, γ = 99.46(2)°, triclinic, space group P1, Z = 4, R = 0.051; 3, C38H50AlNSi, a = 10.413(4) Å, b = 10.585(6) Å, c = 18.281(6) Å, α = 97.75(4)°, β = 96.41(3)°, γ = 118.97(2)°, triclinic, space group P1, Z = 2, R = 0.050; 4, C36H48AlNSi, a= 10.372(3) Å, b= 17.957(8) Å, c = 19.184(8) Å, α = 113.87(3)°, β = 99.23(3)°, γ = 96.71(3)°, triclinic, space group P1, Z = 4, R = 0.045; 5, C46H50AlLiN2, a = 37.78(2) Å, b = 10.635(4) Å, c = 19.237(7) Å, β = 98.19(3)°, monoclinic, space group C2/c, Z = 8, R = 0.056.

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