Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: 13C and 199Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC6H2-2,4,6- Pri3)], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg{(2-SC6H4)2SiMe2}]2

Eric Block; Maria Brito; Michael Gernon; Deborah McGowty; Hyunkyu Kang; Jon Zubieta

doi:10.1021/ic00342a024

Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂

Eric Block, Maria Brito, Michael Gernon, Deborah McGowty, Hyunkyu Kang, Jon Zubieta

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

75 Scopus citations

Abstract

Several series of complexes of the types [MeHg(SR)] and [Hg(SR)₂] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed ¹H, ¹³C, and ¹⁹⁹Hg NMR studies revealed several general trends. The ¹⁹⁹Hg chemical shifts moved upfield in the order [MeHg(SR)] < [Hg(SCR′R″R‴)₂] < [Hg(S-aryl)₂] < [Hg(S-pyridyl)₂], For the [MeHg(SR)] series of complexes, ¹J(Hg-C) correlates with δ(¹³C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ(¹⁹⁹Hg) with steric cone angles for a subset of the complexes. Crystal data are as follows. [CH₃Hg(SC₆H₂-2,4,6·Prⁱ₃)]: triclinic [formula omited], a = 5.962 (1) Å, b = 9.649 (1) Å, c = 15.951 (2) Å, a = 79.60 (1)°, β = 79.58 (1)°, γ = 84.68 (1)°, V= 886.1 (10) Å³, Z = 2, D_calc = 1.69 g cm^-3. Structure solution and refinement based on 2115 reflections (Mo Kα; λ = 0.71073 Å) converged at R = 0.0497. [Hg-(SC₆H₄-2-SiMe₃)₂]: monoclinic A2/a, a = 6.900 (1) Å, b = 12.856 (2) Å,c = 25.974 (5) Å, β = 104.20 (1)°, V= 2234.1 (11) Å³, Z = 4, D_calc = 1.67 g cm^-3, 1277 reflections, R = 0.0313. [Hg(2-SC₅H₃N-3-SiMe₃)₂]: triclinic [formula omited], a = 9.058 (2) Å, b = 9.982 (2) Å, c = 12.639 (3) Å, α = 82.15 (1)°, β = 71.65 (2)°, γ = 79.98 (2)°, V= 1064.3 (10) Å³, Z = 2, D_calc. = 1.77 g cm^-3, 3233 reflections, R = 0.0850. [Hg{(2-SC₆H₄)₂SiMe₂}]₂: triclinic [formula omited], a = 8.680 (2) Å, b = 12.705 (3) Å, c = 15.053 (4) Å, α = 73.94 (2)°, β = 77.56 (2)°, γ = 70.85 (2)°, Z = 2, D_calc = 2.12 g cm^-3, 1350 reflections, R = 0.0854.

Original language	English (US)
Pages (from-to)	3172-3181
Number of pages	10
Journal	Inorganic Chemistry
Volume	29
Issue number	17
DOIs	https://doi.org/10.1021/ic00342a024
State	Published - Aug 1 1990
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00342a024

Fingerprint

Dive into the research topics of 'Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂'. Together they form a unique fingerprint.

Cite this

Block, E., Brito, M., Gernon, M., McGowty, D., Kang, H., & Zubieta, J. (1990). Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂. Inorganic Chemistry, 29(17), 3172-3181. https://doi.org/10.1021/ic00342a024

Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂. / Block, Eric; Brito, Maria; Gernon, Michael et al.
In: Inorganic Chemistry, Vol. 29, No. 17, 01.08.1990, p. 3172-3181.

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

Block, E, Brito, M, Gernon, M, McGowty, D, Kang, H & Zubieta, J 1990, 'Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂', Inorganic Chemistry, vol. 29, no. 17, pp. 3172-3181. https://doi.org/10.1021/ic00342a024

Block E, Brito M, Gernon M, McGowty D, Kang H, Zubieta J. Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂. Inorganic Chemistry. 1990 Aug 1;29(17):3172-3181. doi: 10.1021/ic00342a024

Block, Eric ; Brito, Maria ; Gernon, Michael et al. / Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates : ¹³C and ¹⁹⁹Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC₆H₂-2,4,6- Prⁱ₃)], [Hg(SC₆H₄-2-SiMe₃)₂], [Hg(2-SC₅H₃N-3-SiMe₃)₂], and [Hg{(2-SC₆H₄)₂SiMe₂}]₂. In: Inorganic Chemistry. 1990 ; Vol. 29, No. 17. pp. 3172-3181.

@article{0fb1bfff1d474c279efb0f7f5794885d,

title = "Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: 13C and 199Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC6H2-2,4,6- Pri3)], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg{(2-SC6H4)2SiMe2}]2",

abstract = "Several series of complexes of the types [MeHg(SR)] and [Hg(SR)2] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed 1H, 13C, and 199Hg NMR studies revealed several general trends. The 199Hg chemical shifts moved upfield in the order [MeHg(SR)] < [Hg(SCR′R″R‴)2] < [Hg(S-aryl)2] < [Hg(S-pyridyl)2], For the [MeHg(SR)] series of complexes, 1J(Hg-C) correlates with δ(13C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ(199Hg) with steric cone angles for a subset of the complexes. Crystal data are as follows. [CH3Hg(SC6H2-2,4,6·Pri3)]: triclinic [formula omited], a = 5.962 (1) {\AA}, b = 9.649 (1) {\AA}, c = 15.951 (2) {\AA}, a = 79.60 (1)°, β = 79.58 (1)°, γ = 84.68 (1)°, V= 886.1 (10) {\AA}3, Z = 2, Dcalc = 1.69 g cm-3. Structure solution and refinement based on 2115 reflections (Mo Kα; λ = 0.71073 {\AA}) converged at R = 0.0497. [Hg-(SC6H4-2-SiMe3)2]: monoclinic A2/a, a = 6.900 (1) {\AA}, b = 12.856 (2) {\AA},c = 25.974 (5) {\AA}, β = 104.20 (1)°, V= 2234.1 (11) {\AA}3, Z = 4, Dcalc = 1.67 g cm-3, 1277 reflections, R = 0.0313. [Hg(2-SC5H3N-3-SiMe3)2]: triclinic [formula omited], a = 9.058 (2) {\AA}, b = 9.982 (2) {\AA}, c = 12.639 (3) {\AA}, α = 82.15 (1)°, β = 71.65 (2)°, γ = 79.98 (2)°, V= 1064.3 (10) {\AA}3, Z = 2, Dcalc. = 1.77 g cm-3, 3233 reflections, R = 0.0850. [Hg{(2-SC6H4)2SiMe2}]2: triclinic [formula omited], a = 8.680 (2) {\AA}, b = 12.705 (3) {\AA}, c = 15.053 (4) {\AA}, α = 73.94 (2)°, β = 77.56 (2)°, γ = 70.85 (2)°, Z = 2, Dcalc = 2.12 g cm-3, 1350 reflections, R = 0.0854.",

author = "Eric Block and Maria Brito and Michael Gernon and Deborah McGowty and Hyunkyu Kang and Jon Zubieta",

year = "1990",

month = aug,

day = "1",

doi = "10.1021/ic00342a024",

language = "English (US)",

volume = "29",

pages = "3172--3181",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates

T2 - 13C and 199Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC6H2-2,4,6- Pri3)], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg{(2-SC6H4)2SiMe2}]2

AU - Block, Eric

AU - Brito, Maria

AU - Gernon, Michael

AU - McGowty, Deborah

AU - Kang, Hyunkyu

AU - Zubieta, Jon

PY - 1990/8/1

Y1 - 1990/8/1

N2 - Several series of complexes of the types [MeHg(SR)] and [Hg(SR)2] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed 1H, 13C, and 199Hg NMR studies revealed several general trends. The 199Hg chemical shifts moved upfield in the order [MeHg(SR)] < [Hg(SCR′R″R‴)2] < [Hg(S-aryl)2] < [Hg(S-pyridyl)2], For the [MeHg(SR)] series of complexes, 1J(Hg-C) correlates with δ(13C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ(199Hg) with steric cone angles for a subset of the complexes. Crystal data are as follows. [CH3Hg(SC6H2-2,4,6·Pri3)]: triclinic [formula omited], a = 5.962 (1) Å, b = 9.649 (1) Å, c = 15.951 (2) Å, a = 79.60 (1)°, β = 79.58 (1)°, γ = 84.68 (1)°, V= 886.1 (10) Å3, Z = 2, Dcalc = 1.69 g cm-3. Structure solution and refinement based on 2115 reflections (Mo Kα; λ = 0.71073 Å) converged at R = 0.0497. [Hg-(SC6H4-2-SiMe3)2]: monoclinic A2/a, a = 6.900 (1) Å, b = 12.856 (2) Å,c = 25.974 (5) Å, β = 104.20 (1)°, V= 2234.1 (11) Å3, Z = 4, Dcalc = 1.67 g cm-3, 1277 reflections, R = 0.0313. [Hg(2-SC5H3N-3-SiMe3)2]: triclinic [formula omited], a = 9.058 (2) Å, b = 9.982 (2) Å, c = 12.639 (3) Å, α = 82.15 (1)°, β = 71.65 (2)°, γ = 79.98 (2)°, V= 1064.3 (10) Å3, Z = 2, Dcalc. = 1.77 g cm-3, 3233 reflections, R = 0.0850. [Hg{(2-SC6H4)2SiMe2}]2: triclinic [formula omited], a = 8.680 (2) Å, b = 12.705 (3) Å, c = 15.053 (4) Å, α = 73.94 (2)°, β = 77.56 (2)°, γ = 70.85 (2)°, Z = 2, Dcalc = 2.12 g cm-3, 1350 reflections, R = 0.0854.

AB - Several series of complexes of the types [MeHg(SR)] and [Hg(SR)2] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed 1H, 13C, and 199Hg NMR studies revealed several general trends. The 199Hg chemical shifts moved upfield in the order [MeHg(SR)] < [Hg(SCR′R″R‴)2] < [Hg(S-aryl)2] < [Hg(S-pyridyl)2], For the [MeHg(SR)] series of complexes, 1J(Hg-C) correlates with δ(13C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ(199Hg) with steric cone angles for a subset of the complexes. Crystal data are as follows. [CH3Hg(SC6H2-2,4,6·Pri3)]: triclinic [formula omited], a = 5.962 (1) Å, b = 9.649 (1) Å, c = 15.951 (2) Å, a = 79.60 (1)°, β = 79.58 (1)°, γ = 84.68 (1)°, V= 886.1 (10) Å3, Z = 2, Dcalc = 1.69 g cm-3. Structure solution and refinement based on 2115 reflections (Mo Kα; λ = 0.71073 Å) converged at R = 0.0497. [Hg-(SC6H4-2-SiMe3)2]: monoclinic A2/a, a = 6.900 (1) Å, b = 12.856 (2) Å,c = 25.974 (5) Å, β = 104.20 (1)°, V= 2234.1 (11) Å3, Z = 4, Dcalc = 1.67 g cm-3, 1277 reflections, R = 0.0313. [Hg(2-SC5H3N-3-SiMe3)2]: triclinic [formula omited], a = 9.058 (2) Å, b = 9.982 (2) Å, c = 12.639 (3) Å, α = 82.15 (1)°, β = 71.65 (2)°, γ = 79.98 (2)°, V= 1064.3 (10) Å3, Z = 2, Dcalc. = 1.77 g cm-3, 3233 reflections, R = 0.0850. [Hg{(2-SC6H4)2SiMe2}]2: triclinic [formula omited], a = 8.680 (2) Å, b = 12.705 (3) Å, c = 15.053 (4) Å, α = 73.94 (2)°, β = 77.56 (2)°, γ = 70.85 (2)°, Z = 2, Dcalc = 2.12 g cm-3, 1350 reflections, R = 0.0854.

UR - http://www.scopus.com/inward/record.url?scp=0000328999&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000328999&partnerID=8YFLogxK

U2 - 10.1021/ic00342a024

DO - 10.1021/ic00342a024

M3 - Article

AN - SCOPUS:0000328999

SN - 0020-1669

VL - 29

SP - 3172

EP - 3181

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -