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Conformational Dependence of Through‐Space Tellurium–Tellurium Spin–Spin Coupling in Peri ‐Substituted Bis(Tellurides)
Author(s) -
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
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405599
Subject(s) - acenaphthylene , acenaphthene , aryl , dihedral angle , naphthalene , chemistry , conformational isomerism , tellurium , crystallography , spin (aerodynamics) , carbanion , stereochemistry , molecule , alkyl , organic chemistry , thermodynamics , physics , hydrogen bond
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 CC t configurations, with larger Te(aryl) moieties exclusively imposing the CC t 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 CC t ‐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.