Heterometallic Lanthanide-Group 14 Metal Chalcogenolates

Jongseong Lee; T. J. Emge; J. G. Brennan

doi:10.1021/ic961293t

Heterometallic Lanthanide-Group 14 Metal Chalcogenolates

Jongseong Lee, T. J. Emge, J. G. Brennan

School of Arts and Sciences, Chemistry & Chemical Biology

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Abstract

Heterometallic chalcogenolate compounds containing both lanthanide (Ln) and group 14 metals (M; M = Sn, Pb) form a variety of structures that can be understood in the context of relative metal - chalcogen bond strengths. The compounds (THF)₂Eu(μ₂-SePh)₆Pb₂ (1), [Yb(THF)₆][Sn(SePh)₃]₂ (2), and [(py)₂Eu(2-S-NC₅H₄)₂Sn(2-S-NC ₅H₄)₂]_n (3) have been prepared, and their structures have been established by low-temperature single-crystal X-ray diffraction. Ln-S bonds are found to be relatively insensitive to the presence of a group 14 metal thiolate, whereas Ln-Se bonds are readily distorted upon coordination to Pb(SePh)₂, and cleaved by the addition of the stronger Lewis acid Sn(SePh)₂. The stereochemically active lone pair of electrons on the group 14 metal influences structure, as does the identity of the chalcogenolate. All three compounds show no interaction between the Ln ion and the group 14 metal lone pair. Crystal data (1-3 Mo Kα; -80 to -100°C): 1, triclinic space group Pl̄, a = 10.582(3) Å, b = 12.114(2) Å, c = 18.946(6) Å, α = 89.57(2)°, β= 86.11(4)°, γ = 75.87(2)̊, V= 2350(1)Å³, Z = 2; 2, monoclinic space group P2₁/c, a = 12.961(2) Å, b = 22.768(4) Å, c = 22.560(4) Å, β = 95.04(2)̊, V = 6632(2) Å³, Z = 4; 3, monoclinic space group Cc, a = 20.737(6) Å, b = 9.801(3) Å, c = 18.849(5) Å, β = 125.34(2)̊, V = 3125(2) Å³, Z = 4.

Original language	English (US)
Pages (from-to)	5064-5068
Number of pages	5
Journal	Inorganic Chemistry
Volume	36
Issue number	22
DOIs	https://doi.org/10.1021/ic961293t
State	Published - 1997

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic961293t

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@article{3f01d8c82d164784afdf47e3ef55a059,

title = "Heterometallic Lanthanide-Group 14 Metal Chalcogenolates",

abstract = "Heterometallic chalcogenolate compounds containing both lanthanide (Ln) and group 14 metals (M; M = Sn, Pb) form a variety of structures that can be understood in the context of relative metal - chalcogen bond strengths. The compounds (THF)2Eu(μ2-SePh)6Pb2 (1), [Yb(THF)6][Sn(SePh)3]2 (2), and [(py)2Eu(2-S-NC5H4)2Sn(2-S-NC 5H4)2]n (3) have been prepared, and their structures have been established by low-temperature single-crystal X-ray diffraction. Ln-S bonds are found to be relatively insensitive to the presence of a group 14 metal thiolate, whereas Ln-Se bonds are readily distorted upon coordination to Pb(SePh)2, and cleaved by the addition of the stronger Lewis acid Sn(SePh)2. The stereochemically active lone pair of electrons on the group 14 metal influences structure, as does the identity of the chalcogenolate. All three compounds show no interaction between the Ln ion and the group 14 metal lone pair. Crystal data (1-3 Mo Kα; -80 to -100°C): 1, triclinic space group P{\=l}, a = 10.582(3) {\AA}, b = 12.114(2) {\AA}, c = 18.946(6) {\AA}, α = 89.57(2)°, β= 86.11(4)°, γ = 75.87(2)̊, V= 2350(1){\AA}3, Z = 2; 2, monoclinic space group P21/c, a = 12.961(2) {\AA}, b = 22.768(4) {\AA}, c = 22.560(4) {\AA}, β = 95.04(2)̊, V = 6632(2) {\AA}3, Z = 4; 3, monoclinic space group Cc, a = 20.737(6) {\AA}, b = 9.801(3) {\AA}, c = 18.849(5) {\AA}, β = 125.34(2)̊, V = 3125(2) {\AA}3, Z = 4.",

author = "Jongseong Lee and Emge, {T. J.} and Brennan, {J. G.}",

year = "1997",

doi = "10.1021/ic961293t",

language = "English (US)",

volume = "36",

pages = "5064--5068",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Heterometallic Lanthanide-Group 14 Metal Chalcogenolates

AU - Lee, Jongseong

AU - Emge, T. J.

AU - Brennan, J. G.

PY - 1997

Y1 - 1997

N2 - Heterometallic chalcogenolate compounds containing both lanthanide (Ln) and group 14 metals (M; M = Sn, Pb) form a variety of structures that can be understood in the context of relative metal - chalcogen bond strengths. The compounds (THF)2Eu(μ2-SePh)6Pb2 (1), [Yb(THF)6][Sn(SePh)3]2 (2), and [(py)2Eu(2-S-NC5H4)2Sn(2-S-NC 5H4)2]n (3) have been prepared, and their structures have been established by low-temperature single-crystal X-ray diffraction. Ln-S bonds are found to be relatively insensitive to the presence of a group 14 metal thiolate, whereas Ln-Se bonds are readily distorted upon coordination to Pb(SePh)2, and cleaved by the addition of the stronger Lewis acid Sn(SePh)2. The stereochemically active lone pair of electrons on the group 14 metal influences structure, as does the identity of the chalcogenolate. All three compounds show no interaction between the Ln ion and the group 14 metal lone pair. Crystal data (1-3 Mo Kα; -80 to -100°C): 1, triclinic space group Pl̄, a = 10.582(3) Å, b = 12.114(2) Å, c = 18.946(6) Å, α = 89.57(2)°, β= 86.11(4)°, γ = 75.87(2)̊, V= 2350(1)Å3, Z = 2; 2, monoclinic space group P21/c, a = 12.961(2) Å, b = 22.768(4) Å, c = 22.560(4) Å, β = 95.04(2)̊, V = 6632(2) Å3, Z = 4; 3, monoclinic space group Cc, a = 20.737(6) Å, b = 9.801(3) Å, c = 18.849(5) Å, β = 125.34(2)̊, V = 3125(2) Å3, Z = 4.

AB - Heterometallic chalcogenolate compounds containing both lanthanide (Ln) and group 14 metals (M; M = Sn, Pb) form a variety of structures that can be understood in the context of relative metal - chalcogen bond strengths. The compounds (THF)2Eu(μ2-SePh)6Pb2 (1), [Yb(THF)6][Sn(SePh)3]2 (2), and [(py)2Eu(2-S-NC5H4)2Sn(2-S-NC 5H4)2]n (3) have been prepared, and their structures have been established by low-temperature single-crystal X-ray diffraction. Ln-S bonds are found to be relatively insensitive to the presence of a group 14 metal thiolate, whereas Ln-Se bonds are readily distorted upon coordination to Pb(SePh)2, and cleaved by the addition of the stronger Lewis acid Sn(SePh)2. The stereochemically active lone pair of electrons on the group 14 metal influences structure, as does the identity of the chalcogenolate. All three compounds show no interaction between the Ln ion and the group 14 metal lone pair. Crystal data (1-3 Mo Kα; -80 to -100°C): 1, triclinic space group Pl̄, a = 10.582(3) Å, b = 12.114(2) Å, c = 18.946(6) Å, α = 89.57(2)°, β= 86.11(4)°, γ = 75.87(2)̊, V= 2350(1)Å3, Z = 2; 2, monoclinic space group P21/c, a = 12.961(2) Å, b = 22.768(4) Å, c = 22.560(4) Å, β = 95.04(2)̊, V = 6632(2) Å3, Z = 4; 3, monoclinic space group Cc, a = 20.737(6) Å, b = 9.801(3) Å, c = 18.849(5) Å, β = 125.34(2)̊, V = 3125(2) Å3, Z = 4.

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U2 - 10.1021/ic961293t

DO - 10.1021/ic961293t

M3 - Article

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SN - 0020-1669

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EP - 5068

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Heterometallic Lanthanide-Group 14 Metal Chalcogenolates

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