Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H4)2(SC5H4N)4] (M = Ga, In)

David J. Rose; Yuan Da Chang; Qin Chen; Peter B. Kettler; Jon Zubieta

doi:10.1021/ic00119a019

Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC₅H₄N)₃] (M = Ga, In), [In(SC₅H₃N-3-SiMe₃)₃], and [M₂(OC₂H₄)₂(SC₅H₄N)₄] (M = Ga, In)

David J. Rose, Yuan Da Chang, Qin Chen, Peter B. Kettler, Jon Zubieta

Department of Chemistry

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Abstract

The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC₅H₄N)₃] (1), [In(SC₅H₃N-3-SiMe₃)₃] (2), and [Ga(SC₅H₄N)₃] (5) and of the binuclear alkoxy-bridged derivatives [M₂(OC₂H₅)₂(SC₅H₄N)₄] (M = In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO₃)₃•_xH₂O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl₃ in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl₃ in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl₃ and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na{SC₅H₂N-3,6-(SiMe₂Bu^t)₂}]₆•2(C₂H₅)₂O (7) was isolated and the structure characterized. Crystal data: 1, C₁₅H₁₂N₃S₃In, monoclinic, P2₁ a = 8.779(2) Å, b = 11.614(2) Å, c = 9.397(2) Å, ß = 114.67(3)°, V = 870.7(4) Å³, Z = 2, 2392 reflections with I_o > 3σ (I_o), R = 0.0338; 2, C₂₄H₃₆N₃S₃Si₃In, orthorhombic, Pca2₁, a = 11.645(2) Å, b = 19.741(4) Å, c = 14.040(3) Å, V = 3227(2) Å³, Z = 4, 1930 reflections, R = 0.0464; 3, C₂₄H₂₆N₄O₂S₄ln₂, monoclinic, P₂/n, a = 8.420(2) Å, b= 11.860(2) Å, c = 14.629(3) Å, ß = 101.83(3)°, V = 1429.8(7) Å³, Z = 2, 1699 reflections, R = 0.0296; 5, C₁₅H₁₂N₃S₃Ga, monoclinic, P2₁/n, a = 8.661(2) Å, b = 11.609(4) Å, c = 9.315(2) Å, ß= 115.40(3) Å, Z = 2, 1508 reflections, R = 0.0453; 6, C₂₄H₂₆N₄O₂S₄Ga₂, monoclinic, P2₁/n, a = 8.444(2) Å, b = 11.497(2) Å, c = 14.162(3) Å, ß = 1354.4(7)°, Z = 2, 1513 reflections, R = 0.0349; 7, C₁₂₄H₂₄₈N₆OS₆Si₁₂Na₆, triclinic, P1, a = 16.156(3) Å, c = 17.665(4) Å, α = 118.47(3)°, ß = 92.40(3)°, γ = 114.75(3)°, V = 3757(2) Å³, Z = 1, 5125 reflections, R = 0.0809.

Original language	English (US)
Pages (from-to)	3973-3979
Number of pages	7
Journal	Inorganic Chemistry
Volume	34
Issue number	15
DOIs	https://doi.org/10.1021/ic00119a019
State	Published - Jul 1 1995

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00119a019

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Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC₅H₄N)₃] (M = Ga, In), [In(SC₅H₃N-3-SiMe₃)₃], and [M₂(OC₂H₄)₂(SC₅H₄N)₄] (M = Ga, In). / Rose, David J.; Chang, Yuan Da; Chen, Qin et al.
In: Inorganic Chemistry, Vol. 34, No. 15, 01.07.1995, p. 3973-3979.

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

@article{ac8ae321c49646829d4b1385fe7d0ed1,

title = "Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H4)2(SC5H4N)4] (M = Ga, In)",

abstract = "The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC5H4N)3] (1), [In(SC5H3N-3-SiMe3)3] (2), and [Ga(SC5H4N)3] (5) and of the binuclear alkoxy-bridged derivatives [M2(OC2H5)2(SC5H4N)4] (M = In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO3)3•xH2O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl3 in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl3 in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl3 and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na{SC5H2N-3,6-(SiMe2But)2}]6•2(C2H5)2O (7) was isolated and the structure characterized. Crystal data: 1, C15H12N3S3In, monoclinic, P21 a = 8.779(2) {\AA}, b = 11.614(2) {\AA}, c = 9.397(2) {\AA}, {\ss} = 114.67(3)°, V = 870.7(4) {\AA}3, Z = 2, 2392 reflections with Io > 3σ (Io), R = 0.0338; 2, C24H36N3S3Si3In, orthorhombic, Pca21, a = 11.645(2) {\AA}, b = 19.741(4) {\AA}, c = 14.040(3) {\AA}, V = 3227(2) {\AA}3, Z = 4, 1930 reflections, R = 0.0464; 3, C24H26N4O2S4ln2, monoclinic, P2/n, a = 8.420(2) {\AA}, b= 11.860(2) {\AA}, c = 14.629(3) {\AA}, {\ss} = 101.83(3)°, V = 1429.8(7) {\AA}3, Z = 2, 1699 reflections, R = 0.0296; 5, C15H12N3S3Ga, monoclinic, P21/n, a = 8.661(2) {\AA}, b = 11.609(4) {\AA}, c = 9.315(2) {\AA}, {\ss}= 115.40(3) {\AA}, Z = 2, 1508 reflections, R = 0.0453; 6, C24H26N4O2S4Ga2, monoclinic, P21/n, a = 8.444(2) {\AA}, b = 11.497(2) {\AA}, c = 14.162(3) {\AA}, {\ss} = 1354.4(7)°, Z = 2, 1513 reflections, R = 0.0349; 7, C124H248N6OS6Si12Na6, triclinic, P1, a = 16.156(3) {\AA}, c = 17.665(4) {\AA}, α = 118.47(3)°, {\ss} = 92.40(3)°, γ = 114.75(3)°, V = 3757(2) {\AA}3, Z = 1, 5125 reflections, R = 0.0809.",

author = "Rose, {David J.} and Chang, {Yuan Da} and Qin Chen and Kettler, {Peter B.} and Jon Zubieta",

year = "1995",

month = jul,

day = "1",

doi = "10.1021/ic00119a019",

language = "English (US)",

volume = "34",

pages = "3973--3979",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H4)2(SC5H4N)4] (M = Ga, In)

AU - Rose, David J.

AU - Chang, Yuan Da

AU - Chen, Qin

AU - Kettler, Peter B.

AU - Zubieta, Jon

PY - 1995/7/1

Y1 - 1995/7/1

N2 - The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC5H4N)3] (1), [In(SC5H3N-3-SiMe3)3] (2), and [Ga(SC5H4N)3] (5) and of the binuclear alkoxy-bridged derivatives [M2(OC2H5)2(SC5H4N)4] (M = In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO3)3•xH2O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl3 in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl3 in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl3 and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na{SC5H2N-3,6-(SiMe2But)2}]6•2(C2H5)2O (7) was isolated and the structure characterized. Crystal data: 1, C15H12N3S3In, monoclinic, P21 a = 8.779(2) Å, b = 11.614(2) Å, c = 9.397(2) Å, ß = 114.67(3)°, V = 870.7(4) Å3, Z = 2, 2392 reflections with Io > 3σ (Io), R = 0.0338; 2, C24H36N3S3Si3In, orthorhombic, Pca21, a = 11.645(2) Å, b = 19.741(4) Å, c = 14.040(3) Å, V = 3227(2) Å3, Z = 4, 1930 reflections, R = 0.0464; 3, C24H26N4O2S4ln2, monoclinic, P2/n, a = 8.420(2) Å, b= 11.860(2) Å, c = 14.629(3) Å, ß = 101.83(3)°, V = 1429.8(7) Å3, Z = 2, 1699 reflections, R = 0.0296; 5, C15H12N3S3Ga, monoclinic, P21/n, a = 8.661(2) Å, b = 11.609(4) Å, c = 9.315(2) Å, ß= 115.40(3) Å, Z = 2, 1508 reflections, R = 0.0453; 6, C24H26N4O2S4Ga2, monoclinic, P21/n, a = 8.444(2) Å, b = 11.497(2) Å, c = 14.162(3) Å, ß = 1354.4(7)°, Z = 2, 1513 reflections, R = 0.0349; 7, C124H248N6OS6Si12Na6, triclinic, P1, a = 16.156(3) Å, c = 17.665(4) Å, α = 118.47(3)°, ß = 92.40(3)°, γ = 114.75(3)°, V = 3757(2) Å3, Z = 1, 5125 reflections, R = 0.0809.

AB - The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC5H4N)3] (1), [In(SC5H3N-3-SiMe3)3] (2), and [Ga(SC5H4N)3] (5) and of the binuclear alkoxy-bridged derivatives [M2(OC2H5)2(SC5H4N)4] (M = In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO3)3•xH2O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl3 in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl3 in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl3 and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na{SC5H2N-3,6-(SiMe2But)2}]6•2(C2H5)2O (7) was isolated and the structure characterized. Crystal data: 1, C15H12N3S3In, monoclinic, P21 a = 8.779(2) Å, b = 11.614(2) Å, c = 9.397(2) Å, ß = 114.67(3)°, V = 870.7(4) Å3, Z = 2, 2392 reflections with Io > 3σ (Io), R = 0.0338; 2, C24H36N3S3Si3In, orthorhombic, Pca21, a = 11.645(2) Å, b = 19.741(4) Å, c = 14.040(3) Å, V = 3227(2) Å3, Z = 4, 1930 reflections, R = 0.0464; 3, C24H26N4O2S4ln2, monoclinic, P2/n, a = 8.420(2) Å, b= 11.860(2) Å, c = 14.629(3) Å, ß = 101.83(3)°, V = 1429.8(7) Å3, Z = 2, 1699 reflections, R = 0.0296; 5, C15H12N3S3Ga, monoclinic, P21/n, a = 8.661(2) Å, b = 11.609(4) Å, c = 9.315(2) Å, ß= 115.40(3) Å, Z = 2, 1508 reflections, R = 0.0453; 6, C24H26N4O2S4Ga2, monoclinic, P21/n, a = 8.444(2) Å, b = 11.497(2) Å, c = 14.162(3) Å, ß = 1354.4(7)°, Z = 2, 1513 reflections, R = 0.0349; 7, C124H248N6OS6Si12Na6, triclinic, P1, a = 16.156(3) Å, c = 17.665(4) Å, α = 118.47(3)°, ß = 92.40(3)°, γ = 114.75(3)°, V = 3757(2) Å3, Z = 1, 5125 reflections, R = 0.0809.

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U2 - 10.1021/ic00119a019

DO - 10.1021/ic00119a019

M3 - Article

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SN - 0020-1669

VL - 34

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 15

ER -

Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC₅H₄N)₃] (M = Ga, In), [In(SC₅H₃N-3-SiMe₃)₃], and [M₂(OC₂H₄)₂(SC₅H₄N)₄] (M = Ga, In)

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