1H, 19F, and 13C nuclear magnetic resonance approaches to the barrier to rotation about the Csp2—Csp3 bond in 1,1,1 -trifluoro-2-phenylethane. Proximate coupling constants and molecular orbital computations

The 1H, 19Fand 13C{1H} nuclear magnetic resonance spectra of 1,1,1-trifluoro-2-phenylethane, 1, in CS2–C6D12, acetone-d6, and benzene-d6 solutions, on analysis, yield long-range coupling constants from which are derived the apparent twofold barriers to rotation about the Csp2—Csp3 bonds. The twofold barrier is 9.0(2) kJ/mol, independent of solvent, 4.0 kJ/mol larger than that of ethylbenzene, also independent of solvent. The theoretical barrier heights for the free molecules at the post-Hartree–Fock level of molecular orbital theory (frozen-core MP2/6-31G*) also differ by 4 kJ/mol, but are about 1 kJ/mol higher than the experimental estimates. The perpendicular conformer is the most stable for both molecules. Comparisons are made with the benzyl halides, in which the internal barriers are remarkably sensitive to solvent. A spin–spin coupling constant over five formal bonds, 5J(H, F), involving the ortho protons in 1, is +0.74(2) Hz and is discussed in some detail in terms of its dependence on intenuclear distances (possible through-space interactions). The solvent perturbations of 3J(H, F) and of 2J(C, F) are of opposite sign. Other long-range coupling constants or their absence are also pointed out. For example, those between 19F and 13C nuclei or protons at the meta position are effectively zero; at the para position they are significant. Keywords: 1,1,1-trifluoro-2-phenylethane; 1H, 19F, and 13C NMR; long-range spin-spin coupling constants; through-space 1H, 19F spin–spin coupling constants; internal rotational potential; molecular orbital computations of internal potential.