| Identifier |
8 |
| ¹H NMR (600 MHz, 253K tol-d₈) |
δ = 6.2 (t, ²JH,Fe ~ ²JH,Fd = 71.9 Hz, s in ¹H{¹⁹F}, CF2Hc), 5.9 (dm, ²JH,Fa = 46.5 Hz, 1H, CFHb), 2.29 – 1.40 (m, PaCH2CH3), 1.86 – 1.55 (m, PbCH2CH3), 1.14 – 0.91 (m, PaCH2CH3), 1.03 – 0.91 (m, PbCH2CH3), resonances corresponding to the phosphine ligands are partially overlapping; The phosphorus-proton correlation was confirmed by ¹H-³¹P HMBC NMR spectrum, -10.5 (dq, ²JH,P = 183.4, ²JH,P ~ ¹JH,Rh = 14.4 Hz, d in ¹H{³¹P}, 1H, RhHa) ppm |
| ³¹P{¹H} NMR (121.5 MHz, C₆D₆) |
δ = 16.3 (ddm, ¹JP,Rh = 103.0 Hz, ²JP,Pb = 22.8 Hz, 2P, Pa), -8.3 (dtd, ¹JP,Rh = 85.7 Hz, ³JP,Fa = 42.6 Hz, ²JP,Pa = 22.8 Hz, 1P, Pb) ppm |
| ¹⁹F NMR (282.4 MHz, C₆D₆) |
δ = -71.9 (dm, ddt in ¹⁹F{¹H} NMR spectrum, ²JF,Fc = 145 Hz, ³JF,Fa = 17 Hz; ⁴JF,Fe ~ ⁴JF,Fd = 5 Hz, 1F, Fb), -74.0 (dm, dddd in ¹⁹F{¹H} NMR spectrum, ²JF,Fb = 145 Hz, ³JF,Fa = 15 Hz, ⁴JF,Fd = 5, ⁴JF,Fe = 3 Hz, 1F, Fc), -83.2 (ddt, ²JF,Fd = 175 Hz, , ²JF,Hc = 71 Hz, ⁴JF,Fb ~ ⁴JF,Fc = 5 Hz dt in ¹⁹F{¹H} NMR spectrum; 1F, Fe), -84.3 (dddd, ²JF,Fe = 175 Hz, ²JF,Hc = 72 Hz, ⁴JF,Fb = 5, ⁴JF,Fc = 3 Hz, ddd in ¹⁹F{¹H} NMR spectrum; 1F, Fd), -171.7 (m; 1F, Fa) ppm |
| ³¹P{¹H} NMR assignments, Main |
The ³¹P{¹H} NMR spectrum of complex 8 displays two signals at 16.3 and -8.3 ppm in a 2:1 ratio with phosphorus–rhodium coupling constants (¹JP,Rh = 103.0 and 85.7 Hz, respectively) and phosphorus–phosphorus coupling constants (²JP,P = 22.8 Hz) that are compatible with assignment as a RhIII complex |
| ¹⁹F NMR assignments, Main |
In the ¹⁹F NMR spectrum, two signals resonating as broad doublet of triplets at -71.9, -74.0 ppm can be assigned to the CF2 group in the α-position to the oxygen atom with a geminal fluorine–fluorine coupling constant of ²JF,F = 145 Hz and coupling to the CFH group (³JF,F = 17 Hz and ³JF,F = 15 Hz, respectively). The signal at -74.0 collapses into a doublet of doublet of doublet of doublet in ¹⁹F{¹H} NMR spectrum, displaying an additional coupling to the terminal CF2H moiety (⁴JF,F = 5 Hz, ⁴JF,F = 3 Hz), while the other signal at -71.9 collapses into doublet of doublet of pseudo triplets (⁴JF,F = 5 Hz). The two resonances of the terminal CF2H moiety appear at -83.2 and -84.3 ppm with a geminal fluorine–fluorine coupling constant of ²JF,F = 175 Hz, as well as geminal fluorine–proton coupling constant of ²JF,H = 71 Hz for both signals. The signal at -84.3 appears as a doublet of doublet of doublet of doublets due to the coupling to the above mentioned geminal fluorine and proton atoms, as well as the CF2 moiety (⁴JF,F = 5 Hz, ⁴JF,F = 3 Hz), while the signal at -83.2 exhibit a doublet of doublet of pseudo triplets (⁴JF,F = 5 Hz). Finally, the signal corresponding to the CFH group is shifted to higher field and appears at -171.7 ppm as a multiplet |
| ¹H NMR assignments, Main |
In the ¹H NMR spectrum, the most characteristic signal belongs to the hydrido ligand at -10.5 ppm, which appears as a doublet of quartet with a trans hydride−phosphine coupling constant of 183.4 Hz as well as coupling to the rhodium and the cis phosphines (¹JH,Rh ~ ²JH,P = 14.4 Hz), which collapses into a doublet in the ¹H{³¹P} NMR spectrum. The signal of the CFH group is observed in ¹H NMR spectrum (600 MHz) at 5.9 ppm as a doublet of multiplets with a geminal fluorine–proton coupling constant of ²JH,F = 46.5 Hz. A signal corresponding to the terminal CF2H group resonates at 6.4 ppm as a triplet (²JH,F = 70.9 Hz), which collapses to a singlet in ¹H{¹⁹F} NMR spectrum |