Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)

Fergus Ross Knight; Louise Diamond; Kasun Sankalpa Athukorala Arachchige; Paula Sanz Camacho; Rebecca Amy Michele Randall; Sharon Elizabeth Ashbrook; Michael Buehl; Alexandra Martha Zoya Slawin; J Derek Woollins

doi:10.1002/chem.201405599

Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)

Fergus Ross Knight, Louise Diamond, Kasun Sankalpa Athukorala Arachchige, Paula Sanz Camacho, Rebecca Amy Michele Randall, Sharon Elizabeth Ashbrook, Michael Buehl, Alexandra Martha Zoya Slawin, J Derek Woollins

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Abstract

Three related series of peri‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)₂ (Nap=naphthalene‐1,8‐diyl N; Acenap=acenaphthene‐5,6‐diyl A; Aceyl=acenaphthylene‐5,6‐diyl Ay; Y=Ph 1; Fp 2; Tol 3; An‐p 4; An‐o 5; Tp 6; Mes 7; Tip 8) have been synthesised and their solid‐state structures determined by X‐ray crystallography. Molecular conformations were classified as a function of the two C9‐C‐Te‐C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J(¹²⁵Te,¹²⁵Te) spin–spin coupling constants between 3289–3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050–2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through‐space coupling is supported by DFT calculations.

Original language	English
Pages (from-to)	3613-3627
Journal	Chemistry - A European Journal
Volume	21
Issue number	9
Early online date	22 Dec 2014
DOIs	https://doi.org/10.1002/chem.201405599
Publication status	Published - 16 Feb 2015

Keywords

Bis(tellurides)
Conformational dependence
DFT calculations
NMR spectroscopy
Spin–spin coupling
X-ray crystallography

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10.1002/chem.201405599

Woollins_2014_CEJ_Conformational_AM
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Knight, F. R., Diamond, L. M., Arachchige, K. S. A., Sanz Camacho, P., Randall, R. A. M., Ashbrook, S. E., Bühl, M., Slawin, A. M. Z. and Woollins, J. D. (2014), Conformational Dependence of Through-Space Tellurium–Tellurium Spin–Spin Coupling in Peri-Substituted Bis(Tellurides). Chem. Eur. J.., which has been published in final form at http://dx.doi.org/10.1002/chem.201405599
Accepted author manuscript, 1.21 MB

Cite this

Knight, F. R., Diamond, L., Athukorala Arachchige, K. S., Sanz Camacho, P., Randall, R. A. M., Ashbrook, S. E., Buehl, M., Slawin, A. M. Z., & Woollins, J. D. (2015). Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides). Chemistry - A European Journal, 21(9), 3613-3627. https://doi.org/10.1002/chem.201405599

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title = "Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)",

abstract = "Three related series of peri‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap=naphthalene‐1,8‐diyl N; Acenap=acenaphthene‐5,6‐diyl A; Aceyl=acenaphthylene‐5,6‐diyl Ay; Y=Ph 1; Fp 2; Tol 3; An‐p 4; An‐o 5; Tp 6; Mes 7; Tip 8) have been synthesised and their solid‐state structures determined by X‐ray crystallography. Molecular conformations were classified as a function of the two C9‐C‐Te‐C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J(125Te,125Te) spin–spin coupling constants between 3289–3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050–2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through‐space coupling is supported by DFT calculations.",

keywords = "Bis(tellurides), Conformational dependence, DFT calculations, NMR spectroscopy, Spin–spin coupling, X-ray crystallography",

author = "Knight, {Fergus Ross} and Louise Diamond and {Athukorala Arachchige}, {Kasun Sankalpa} and {Sanz Camacho}, Paula and Randall, {Rebecca Amy Michele} and Ashbrook, {Sharon Elizabeth} and Michael Buehl and Slawin, {Alexandra Martha Zoya} and Woollins, {J Derek}",

note = "The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC). M.B. wishes to thank EaStCHEM and the University of St Andrews for support.",

year = "2015",

month = feb,

day = "16",

doi = "10.1002/chem.201405599",

language = "English",

volume = "21",

pages = "3613--3627",

journal = "Chemistry - A European Journal",

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T1 - Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)

AU - Knight, Fergus Ross

AU - Diamond, Louise

AU - Athukorala Arachchige, Kasun Sankalpa

AU - Sanz Camacho, Paula

AU - Randall, Rebecca Amy Michele

AU - Ashbrook, Sharon Elizabeth

AU - Buehl, Michael

AU - Slawin, Alexandra Martha Zoya

AU - Woollins, J Derek

N1 - The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC). M.B. wishes to thank EaStCHEM and the University of St Andrews for support.

PY - 2015/2/16

Y1 - 2015/2/16

N2 - Three related series of peri‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap=naphthalene‐1,8‐diyl N; Acenap=acenaphthene‐5,6‐diyl A; Aceyl=acenaphthylene‐5,6‐diyl Ay; Y=Ph 1; Fp 2; Tol 3; An‐p 4; An‐o 5; Tp 6; Mes 7; Tip 8) have been synthesised and their solid‐state structures determined by X‐ray crystallography. Molecular conformations were classified as a function of the two C9‐C‐Te‐C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J(125Te,125Te) spin–spin coupling constants between 3289–3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050–2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through‐space coupling is supported by DFT calculations.

AB - Three related series of peri‐substituted bis(tellurides) bearing naphthalene, acenaphthene and acenaphthylene backbones (Nap/Acenap/Aceyl(TeY)2 (Nap=naphthalene‐1,8‐diyl N; Acenap=acenaphthene‐5,6‐diyl A; Aceyl=acenaphthylene‐5,6‐diyl Ay; Y=Ph 1; Fp 2; Tol 3; An‐p 4; An‐o 5; Tp 6; Mes 7; Tip 8) have been synthesised and their solid‐state structures determined by X‐ray crystallography. Molecular conformations were classified as a function of the two C9‐C‐Te‐C(Y) dihedral angles (θ); in the solid all members adopt AB or CCt configurations, with larger Te(aryl) moieties exclusively imposing the CCt variant. Exceptionally large J(125Te,125Te) spin–spin coupling constants between 3289–3848 Hz were obtained for compounds substituted by bulky Te(aryl) groups, implying these species are locked in a CCt‐type conformation. In contrast, compounds incorporating smaller Te(aryl) moieties are predicted to be rather dynamic in solution and afford much smaller J values (2050–2676 Hz), characteristic of greater populations of AB conformers with lower couplings. This conformational dependence of through‐space coupling is supported by DFT calculations.

KW - Bis(tellurides)

KW - Conformational dependence

KW - DFT calculations

KW - NMR spectroscopy

KW - Spin–spin coupling

KW - X-ray crystallography

UR - https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201405599#support-information-section

U2 - 10.1002/chem.201405599

DO - 10.1002/chem.201405599

M3 - Article

C2 - 25533475

SN - 0947-6539

VL - 21

SP - 3613

EP - 3627

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 9

ER -

Conformational dependence of through-space tellurium-tellurium spin-spin coupling in peri-substituted bis(tellurides)

Abstract

Keywords

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