Correlation of structure and internal dynamics for (tris(2,6-dimethoxyphenyl)methyl)tin trihalides: A homologous series of seven-coordinate tin compounds

Stanley Dostal, Scott J. Stoudt, Phil Fanwick, Washington F. Sereatan, Bart Kahr, James E. Jackson

Research output: Contribution to journalArticle

Abstract

Reaction of tris(2,6-dimethoxyphenyl)methyl cation and the stannous halides produced a series of SnX3 (1, X = F; 2, X = Cl; 3, X = Br; 4, X = I) derivatives of the triarylmethyl. These species constitute a homologous series of heptacoordinate tin compounds. Crystals of 1 are monoclinic, space group P21/c: a = 9.8087(5) Å, b = 16.081(3) Å, c = 15.864(2) Å, β = 106.120(6)°, Z = 4. Crystals of 2 are orthorhombic, space group P212121, a = 11.622(2) Å, b = 15.192(2) Å, c = 33.379(3) Å, Z = 8. The asymmetric unit contains two independent, heterochiral molecules and one molecule of diethyl ether. Crystals of 3 are triclinic, space group P1: a = 10.049(1) Å, b = 10.7709(9) Å, c = 14.996(3) Å, a = 93.18(1)°, β = 104.77(1)°, γ = 116.263(9)°, Z = 2. The tin atoms are covalently bound to three halogens and the central carbon of the triarylmethyl unit; their association with the three near methoxy groups raises their coordination number to seven. Methoxy group site exchange barriers were determined for 1-4 by variable temperature NMR spectroscopy and/or by the saturation spin transfer method: ΔG‡: 1, 83 kJ mol-1; 2, 71 kJ mol-1; 3, 65/64 kJ mol-1 (both methods); 4, 59 kJ mol-1. Since aryl ring rotation requires concomitant Sn-O bond breaking, the activation energies serve to measure the relative strengths of the Sn ligation by the ether oxygens. The trend observed (F > Cl > Br > I) correlates well with progressive molecular structure changes among 1, 2, and 3 and with expectations from the relative Lewis acidities of the tin halides. The order of the 119Sn NMR chemical shifts for 2-4 also conforms to expectations based on halide electronegativity, but shows a strong leveling effect which is attributed to coordination by the ether tripods.

Original languageEnglish (US)
Pages (from-to)2284-2291
Number of pages8
JournalOrganometallics
Volume12
Issue number6
StatePublished - 1993

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Tin Compounds
tin compounds
Tin
Ether
tin
Crystals
halides
Electronegativity
Molecules
Halogens
Chemical shift
ethers
Acidity
Molecular structure
Nuclear magnetic resonance spectroscopy
Cations
crystals
Carbon
tripods
Activation energy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Correlation of structure and internal dynamics for (tris(2,6-dimethoxyphenyl)methyl)tin trihalides : A homologous series of seven-coordinate tin compounds. / Dostal, Stanley; Stoudt, Scott J.; Fanwick, Phil; Sereatan, Washington F.; Kahr, Bart; Jackson, James E.

In: Organometallics, Vol. 12, No. 6, 1993, p. 2284-2291.

Research output: Contribution to journalArticle

Dostal, Stanley ; Stoudt, Scott J. ; Fanwick, Phil ; Sereatan, Washington F. ; Kahr, Bart ; Jackson, James E. / Correlation of structure and internal dynamics for (tris(2,6-dimethoxyphenyl)methyl)tin trihalides : A homologous series of seven-coordinate tin compounds. In: Organometallics. 1993 ; Vol. 12, No. 6. pp. 2284-2291.
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abstract = "Reaction of tris(2,6-dimethoxyphenyl)methyl cation and the stannous halides produced a series of SnX3 (1, X = F; 2, X = Cl; 3, X = Br; 4, X = I) derivatives of the triarylmethyl. These species constitute a homologous series of heptacoordinate tin compounds. Crystals of 1 are monoclinic, space group P21/c: a = 9.8087(5) {\AA}, b = 16.081(3) {\AA}, c = 15.864(2) {\AA}, β = 106.120(6)°, Z = 4. Crystals of 2 are orthorhombic, space group P212121, a = 11.622(2) {\AA}, b = 15.192(2) {\AA}, c = 33.379(3) {\AA}, Z = 8. The asymmetric unit contains two independent, heterochiral molecules and one molecule of diethyl ether. Crystals of 3 are triclinic, space group P1: a = 10.049(1) {\AA}, b = 10.7709(9) {\AA}, c = 14.996(3) {\AA}, a = 93.18(1)°, β = 104.77(1)°, γ = 116.263(9)°, Z = 2. The tin atoms are covalently bound to three halogens and the central carbon of the triarylmethyl unit; their association with the three near methoxy groups raises their coordination number to seven. Methoxy group site exchange barriers were determined for 1-4 by variable temperature NMR spectroscopy and/or by the saturation spin transfer method: ΔG‡: 1, 83 kJ mol-1; 2, 71 kJ mol-1; 3, 65/64 kJ mol-1 (both methods); 4, 59 kJ mol-1. Since aryl ring rotation requires concomitant Sn-O bond breaking, the activation energies serve to measure the relative strengths of the Sn ligation by the ether oxygens. The trend observed (F > Cl > Br > I) correlates well with progressive molecular structure changes among 1, 2, and 3 and with expectations from the relative Lewis acidities of the tin halides. The order of the 119Sn NMR chemical shifts for 2-4 also conforms to expectations based on halide electronegativity, but shows a strong leveling effect which is attributed to coordination by the ether tripods.",
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T1 - Correlation of structure and internal dynamics for (tris(2,6-dimethoxyphenyl)methyl)tin trihalides

T2 - A homologous series of seven-coordinate tin compounds

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AU - Stoudt, Scott J.

AU - Fanwick, Phil

AU - Sereatan, Washington F.

AU - Kahr, Bart

AU - Jackson, James E.

PY - 1993

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N2 - Reaction of tris(2,6-dimethoxyphenyl)methyl cation and the stannous halides produced a series of SnX3 (1, X = F; 2, X = Cl; 3, X = Br; 4, X = I) derivatives of the triarylmethyl. These species constitute a homologous series of heptacoordinate tin compounds. Crystals of 1 are monoclinic, space group P21/c: a = 9.8087(5) Å, b = 16.081(3) Å, c = 15.864(2) Å, β = 106.120(6)°, Z = 4. Crystals of 2 are orthorhombic, space group P212121, a = 11.622(2) Å, b = 15.192(2) Å, c = 33.379(3) Å, Z = 8. The asymmetric unit contains two independent, heterochiral molecules and one molecule of diethyl ether. Crystals of 3 are triclinic, space group P1: a = 10.049(1) Å, b = 10.7709(9) Å, c = 14.996(3) Å, a = 93.18(1)°, β = 104.77(1)°, γ = 116.263(9)°, Z = 2. The tin atoms are covalently bound to three halogens and the central carbon of the triarylmethyl unit; their association with the three near methoxy groups raises their coordination number to seven. Methoxy group site exchange barriers were determined for 1-4 by variable temperature NMR spectroscopy and/or by the saturation spin transfer method: ΔG‡: 1, 83 kJ mol-1; 2, 71 kJ mol-1; 3, 65/64 kJ mol-1 (both methods); 4, 59 kJ mol-1. Since aryl ring rotation requires concomitant Sn-O bond breaking, the activation energies serve to measure the relative strengths of the Sn ligation by the ether oxygens. The trend observed (F > Cl > Br > I) correlates well with progressive molecular structure changes among 1, 2, and 3 and with expectations from the relative Lewis acidities of the tin halides. The order of the 119Sn NMR chemical shifts for 2-4 also conforms to expectations based on halide electronegativity, but shows a strong leveling effect which is attributed to coordination by the ether tripods.

AB - Reaction of tris(2,6-dimethoxyphenyl)methyl cation and the stannous halides produced a series of SnX3 (1, X = F; 2, X = Cl; 3, X = Br; 4, X = I) derivatives of the triarylmethyl. These species constitute a homologous series of heptacoordinate tin compounds. Crystals of 1 are monoclinic, space group P21/c: a = 9.8087(5) Å, b = 16.081(3) Å, c = 15.864(2) Å, β = 106.120(6)°, Z = 4. Crystals of 2 are orthorhombic, space group P212121, a = 11.622(2) Å, b = 15.192(2) Å, c = 33.379(3) Å, Z = 8. The asymmetric unit contains two independent, heterochiral molecules and one molecule of diethyl ether. Crystals of 3 are triclinic, space group P1: a = 10.049(1) Å, b = 10.7709(9) Å, c = 14.996(3) Å, a = 93.18(1)°, β = 104.77(1)°, γ = 116.263(9)°, Z = 2. The tin atoms are covalently bound to three halogens and the central carbon of the triarylmethyl unit; their association with the three near methoxy groups raises their coordination number to seven. Methoxy group site exchange barriers were determined for 1-4 by variable temperature NMR spectroscopy and/or by the saturation spin transfer method: ΔG‡: 1, 83 kJ mol-1; 2, 71 kJ mol-1; 3, 65/64 kJ mol-1 (both methods); 4, 59 kJ mol-1. Since aryl ring rotation requires concomitant Sn-O bond breaking, the activation energies serve to measure the relative strengths of the Sn ligation by the ether oxygens. The trend observed (F > Cl > Br > I) correlates well with progressive molecular structure changes among 1, 2, and 3 and with expectations from the relative Lewis acidities of the tin halides. The order of the 119Sn NMR chemical shifts for 2-4 also conforms to expectations based on halide electronegativity, but shows a strong leveling effect which is attributed to coordination by the ether tripods.

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