Conformational Dependence of Through‐Space Tellurium–Tellurium Spin–Spin Coupling in Peri‐Substituted Bis(Tellurides)
Year: 2014
Type: article
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((125)Te,(125)Te) 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.
Source: Chemistry - A European Journal
Institution: University of St Andrews
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
Awards: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation, Small items of research equipment at the University of St Andrews. Supporting a new generation of Physical Sciences Research., G7012131025, EPSRC UK National Service for Computational Chemistry Software
OpenAlex ID: W2091103457