Synthesis and structure of unassociated mono-, di-, and trithiolate derivatives of aluminum and gallium: Investigation of Al-S and Ga-S π-bonding

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

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Abstract

The synthesis and characterization of several sterically crowded aluminum and gallium thiolates are described. The major reason for these studies was the investigation of the possible occurrence of .-bonding in Al-S and Ga-S bonds and the determination of the steric requirements for the isolation of monomeric heavier main group 3 thiolates in the solid state. The compounds examined were RA1(SMes*)2 (R = n-Bu, 1; t-Bu, 2), Mes*2GaSR (Mes* = 2,4,6-t-Bu3C6H2, R = Me, 3; Ph, 4), n-BuGa(SMes*)2, (5) (t-Bu2AlSTrip)2 (6) (Trip = 2,4,6-t-Pr3C6H2), (THF)Al(STrip)3 (7). They were characterized by X-ray crystallography (1-3, 5-7) and by NMR and IR spectroscopy. The data indicate that the M-S, p-p, π-bonding is weak and has an upper limit of 8-9 kcal mol-1. Restricted rotation around an M-S bond was detected only in the cases of Mes*2GaSMe (3) and Mes*2-GaSPh (4). Crystal data at 130 K with Mo Kα (λ = 0.710 69 Å) (2, 5-7) or Cu Kα (λ= 1.541 78 Å) (1, 3) radiation; 1, n-BuAl(SMes*)2, C40H67AlS2, a = 18.563(5) Å, b = 27.171(11) Å, c = 32.089(4) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.087 for 6746 (I > 2σ(I)) data; 2, t-BuAl(SMes*)2, C40H67AlS2, a = 17.375(9) Å, b = 27.982(10) Å, c = 17.868(8) Å, β = 112.29(2)°, Z = 8 (two independent molecules), monoclinic, space group P21/c, R = 0.082 for 8425 (I > 2σ(I)) reflections; 3, Mes*2GaSMe, C37H61-GaS, a = 33.654(8) Å, b = 10.433(4) Å, c = 20.258(8) Å, Z = 8, orthorhombic, space group Pbcn, R = 0.066 for 3164 (I > 2σ(I)) reflections; 5, n-BuGa(SMes*)2, C40H67GaS2, a = 18.521(8) Å, b = 27.342(10) Å, c = 32.046(12) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.144 for 3297 (I > 2σ(I)) reflections; 6, (t-Bu2AlSTrip)2, C46H82Al2S2, a = 20.820(8) Å, b = 14.598(6) Å, c = 16.118(4) Å, Z = 4, orthorhombic, space group Pna21, R = 0.062 for 2469 (I > 2.5σ(I)) data; 7, (THF)Al(STrip)3·0.5C6H14, C52H84-AlOS3, a = 15.589(6) Å, b = 13.622(5) Å, c = 26.308(12) Å, β = 99.88(2)°, Z = 4, monoclinic, space group P21/c, R = 0.075 for 5697 (I > 3σ(I)) data.

Original languageEnglish (US)
Pages (from-to)2593-2599
Number of pages7
JournalInorganic Chemistry
Volume34
Issue number10
StatePublished - 1995
Externally publishedYes

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Gallium
Aluminum
gallium
Derivatives
aluminum
Molecules
synthesis
X ray crystallography
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
strip
Radiation
Crystals
molecules
crystallography
isolation
occurrences
solid state
requirements
nuclear magnetic resonance

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  • Inorganic Chemistry

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Synthesis and structure of unassociated mono-, di-, and trithiolate derivatives of aluminum and gallium : Investigation of Al-S and Ga-S π-bonding. / Wehmschulte, Rudolf J.; Ruhlandt, Karin; Power, Philip P.

In: Inorganic Chemistry, Vol. 34, No. 10, 1995, p. 2593-2599.

Research output: Contribution to journalArticle

@article{b562a54affc8430099e8b9565f77f05c,
title = "Synthesis and structure of unassociated mono-, di-, and trithiolate derivatives of aluminum and gallium: Investigation of Al-S and Ga-S π-bonding",
abstract = "The synthesis and characterization of several sterically crowded aluminum and gallium thiolates are described. The major reason for these studies was the investigation of the possible occurrence of .-bonding in Al-S and Ga-S bonds and the determination of the steric requirements for the isolation of monomeric heavier main group 3 thiolates in the solid state. The compounds examined were RA1(SMes*)2 (R = n-Bu, 1; t-Bu, 2), Mes*2GaSR (Mes* = 2,4,6-t-Bu3C6H2, R = Me, 3; Ph, 4), n-BuGa(SMes*)2, (5) (t-Bu2AlSTrip)2 (6) (Trip = 2,4,6-t-Pr3C6H2), (THF)Al(STrip)3 (7). They were characterized by X-ray crystallography (1-3, 5-7) and by NMR and IR spectroscopy. The data indicate that the M-S, p-p, π-bonding is weak and has an upper limit of 8-9 kcal mol-1. Restricted rotation around an M-S bond was detected only in the cases of Mes*2GaSMe (3) and Mes*2-GaSPh (4). Crystal data at 130 K with Mo Kα (λ = 0.710 69 {\AA}) (2, 5-7) or Cu Kα (λ= 1.541 78 {\AA}) (1, 3) radiation; 1, n-BuAl(SMes*)2, C40H67AlS2, a = 18.563(5) {\AA}, b = 27.171(11) {\AA}, c = 32.089(4) {\AA}, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.087 for 6746 (I > 2σ(I)) data; 2, t-BuAl(SMes*)2, C40H67AlS2, a = 17.375(9) {\AA}, b = 27.982(10) {\AA}, c = 17.868(8) {\AA}, β = 112.29(2)°, Z = 8 (two independent molecules), monoclinic, space group P21/c, R = 0.082 for 8425 (I > 2σ(I)) reflections; 3, Mes*2GaSMe, C37H61-GaS, a = 33.654(8) {\AA}, b = 10.433(4) {\AA}, c = 20.258(8) {\AA}, Z = 8, orthorhombic, space group Pbcn, R = 0.066 for 3164 (I > 2σ(I)) reflections; 5, n-BuGa(SMes*)2, C40H67GaS2, a = 18.521(8) {\AA}, b = 27.342(10) {\AA}, c = 32.046(12) {\AA}, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.144 for 3297 (I > 2σ(I)) reflections; 6, (t-Bu2AlSTrip)2, C46H82Al2S2, a = 20.820(8) {\AA}, b = 14.598(6) {\AA}, c = 16.118(4) {\AA}, Z = 4, orthorhombic, space group Pna21, R = 0.062 for 2469 (I > 2.5σ(I)) data; 7, (THF)Al(STrip)3·0.5C6H14, C52H84-AlOS3, a = 15.589(6) {\AA}, b = 13.622(5) {\AA}, c = 26.308(12) {\AA}, β = 99.88(2)°, Z = 4, monoclinic, space group P21/c, R = 0.075 for 5697 (I > 3σ(I)) data.",
author = "Wehmschulte, {Rudolf J.} and Karin Ruhlandt and Power, {Philip P.}",
year = "1995",
language = "English (US)",
volume = "34",
pages = "2593--2599",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Synthesis and structure of unassociated mono-, di-, and trithiolate derivatives of aluminum and gallium

T2 - Investigation of Al-S and Ga-S π-bonding

AU - Wehmschulte, Rudolf J.

AU - Ruhlandt, Karin

AU - Power, Philip P.

PY - 1995

Y1 - 1995

N2 - The synthesis and characterization of several sterically crowded aluminum and gallium thiolates are described. The major reason for these studies was the investigation of the possible occurrence of .-bonding in Al-S and Ga-S bonds and the determination of the steric requirements for the isolation of monomeric heavier main group 3 thiolates in the solid state. The compounds examined were RA1(SMes*)2 (R = n-Bu, 1; t-Bu, 2), Mes*2GaSR (Mes* = 2,4,6-t-Bu3C6H2, R = Me, 3; Ph, 4), n-BuGa(SMes*)2, (5) (t-Bu2AlSTrip)2 (6) (Trip = 2,4,6-t-Pr3C6H2), (THF)Al(STrip)3 (7). They were characterized by X-ray crystallography (1-3, 5-7) and by NMR and IR spectroscopy. The data indicate that the M-S, p-p, π-bonding is weak and has an upper limit of 8-9 kcal mol-1. Restricted rotation around an M-S bond was detected only in the cases of Mes*2GaSMe (3) and Mes*2-GaSPh (4). Crystal data at 130 K with Mo Kα (λ = 0.710 69 Å) (2, 5-7) or Cu Kα (λ= 1.541 78 Å) (1, 3) radiation; 1, n-BuAl(SMes*)2, C40H67AlS2, a = 18.563(5) Å, b = 27.171(11) Å, c = 32.089(4) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.087 for 6746 (I > 2σ(I)) data; 2, t-BuAl(SMes*)2, C40H67AlS2, a = 17.375(9) Å, b = 27.982(10) Å, c = 17.868(8) Å, β = 112.29(2)°, Z = 8 (two independent molecules), monoclinic, space group P21/c, R = 0.082 for 8425 (I > 2σ(I)) reflections; 3, Mes*2GaSMe, C37H61-GaS, a = 33.654(8) Å, b = 10.433(4) Å, c = 20.258(8) Å, Z = 8, orthorhombic, space group Pbcn, R = 0.066 for 3164 (I > 2σ(I)) reflections; 5, n-BuGa(SMes*)2, C40H67GaS2, a = 18.521(8) Å, b = 27.342(10) Å, c = 32.046(12) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.144 for 3297 (I > 2σ(I)) reflections; 6, (t-Bu2AlSTrip)2, C46H82Al2S2, a = 20.820(8) Å, b = 14.598(6) Å, c = 16.118(4) Å, Z = 4, orthorhombic, space group Pna21, R = 0.062 for 2469 (I > 2.5σ(I)) data; 7, (THF)Al(STrip)3·0.5C6H14, C52H84-AlOS3, a = 15.589(6) Å, b = 13.622(5) Å, c = 26.308(12) Å, β = 99.88(2)°, Z = 4, monoclinic, space group P21/c, R = 0.075 for 5697 (I > 3σ(I)) data.

AB - The synthesis and characterization of several sterically crowded aluminum and gallium thiolates are described. The major reason for these studies was the investigation of the possible occurrence of .-bonding in Al-S and Ga-S bonds and the determination of the steric requirements for the isolation of monomeric heavier main group 3 thiolates in the solid state. The compounds examined were RA1(SMes*)2 (R = n-Bu, 1; t-Bu, 2), Mes*2GaSR (Mes* = 2,4,6-t-Bu3C6H2, R = Me, 3; Ph, 4), n-BuGa(SMes*)2, (5) (t-Bu2AlSTrip)2 (6) (Trip = 2,4,6-t-Pr3C6H2), (THF)Al(STrip)3 (7). They were characterized by X-ray crystallography (1-3, 5-7) and by NMR and IR spectroscopy. The data indicate that the M-S, p-p, π-bonding is weak and has an upper limit of 8-9 kcal mol-1. Restricted rotation around an M-S bond was detected only in the cases of Mes*2GaSMe (3) and Mes*2-GaSPh (4). Crystal data at 130 K with Mo Kα (λ = 0.710 69 Å) (2, 5-7) or Cu Kα (λ= 1.541 78 Å) (1, 3) radiation; 1, n-BuAl(SMes*)2, C40H67AlS2, a = 18.563(5) Å, b = 27.171(11) Å, c = 32.089(4) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.087 for 6746 (I > 2σ(I)) data; 2, t-BuAl(SMes*)2, C40H67AlS2, a = 17.375(9) Å, b = 27.982(10) Å, c = 17.868(8) Å, β = 112.29(2)°, Z = 8 (two independent molecules), monoclinic, space group P21/c, R = 0.082 for 8425 (I > 2σ(I)) reflections; 3, Mes*2GaSMe, C37H61-GaS, a = 33.654(8) Å, b = 10.433(4) Å, c = 20.258(8) Å, Z = 8, orthorhombic, space group Pbcn, R = 0.066 for 3164 (I > 2σ(I)) reflections; 5, n-BuGa(SMes*)2, C40H67GaS2, a = 18.521(8) Å, b = 27.342(10) Å, c = 32.046(12) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.144 for 3297 (I > 2σ(I)) reflections; 6, (t-Bu2AlSTrip)2, C46H82Al2S2, a = 20.820(8) Å, b = 14.598(6) Å, c = 16.118(4) Å, Z = 4, orthorhombic, space group Pna21, R = 0.062 for 2469 (I > 2.5σ(I)) data; 7, (THF)Al(STrip)3·0.5C6H14, C52H84-AlOS3, a = 15.589(6) Å, b = 13.622(5) Å, c = 26.308(12) Å, β = 99.88(2)°, Z = 4, monoclinic, space group P21/c, R = 0.075 for 5697 (I > 3σ(I)) data.

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