Conformational Dependence of Through-Space Tellurium-Tellurium Spin-Spin Coupling in Peri-Substituted Bis(Tellurides)

• Published in: Chemistry : a European journal 2015-02, Vol.21 (9), p.3613-3627
• Main Authors: Knight, Fergus R., Diamond, Louise M., Arachchige, Kasun S. Athukorala, Sanz Camacho, Paula, Randall, Rebecca A. M., Ashbrook, Sharon E., Bühl, Michael, Slawin, Alexandra M. Z., Woollins, J. Derek
• Format: Article
• Language: English
• Subjects: bis(tellurides); Chemistry; conformational dependence; Constants; Couplings; Crystallography; DFT calculations; Filled plastics; Mathematical analysis; NMR spectroscopy; Spin-spin coupling; X-ray crystallography; X-rays
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201405599

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. X‐ray crystallography, NMR spectroscopy and DFT calculations have been used to investigate the conformational dependence of through‐space J(125Te,125Te) spin–spin coupling in three related series of peri‐substituted bis(tellurides); Nap/Acenap/Aceyl(TeY)2 (Nap=naphthalene‐1,8‐diyl; Acenap= acenaphthene‐5,6‐diyl; Aceyl=acenaphthylene‐5,6‐diyl; Y=Ph; Fp; Tol; An‐p; An‐o; Tp; Mes; Tip). WBI=Wiberg bond index.