Content
Tautomerization of 2-naphthol-AlCl3 complex
C-Protonation of 2-naphthol-AlCl3 complexes CE and CZ
Reaction of 2-naphthol-AlCl3 complex with benzene
Binol-AlCl3 complexes
Protonated BINOL
Diprotonated BINOL
Protonated CO-tautomer of Binol-AlCl3 complex
Transition states of racemization of BINOL

Tautomerization of 2-naphthol-AlCl3 complex

The geometries of prereaction comlexes and transition states were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


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Click on energy level to view 3D structure in browser (run JSmol) ==>

-5.97 -5.97 -4.81 -4.81 0.00 0.00 0.04 0.04 13.91 13.91 -5.26 -5.26 -2.56 -2.56 0.00 0.00 0.14 0.14 0.32 0.32 1.15 1.15 48.69 48.69

IRC (concatenated xyz) from OE-CE and OE-CE_HCl

C-Protonation of 2-naphthol-AlCl3 complexes CE and CZ

0.00 0.00 2.37 2.37 4.94 4.94 6.03 6.03 6.78 6.78 6.80 6.80 7.10 7.10 11.04 11.04 11.51 11.51 14.35 14.35 15.72 15.72 28.26 28.26

Reaction of 2-naphthol-AlCl3 complex with benzene

Conformational analysis of the reaction products (Ph-E and Ph-Z) was performed with the computer program package ChemAxon Marvin (conformers plugin).
The geometries of all the conformers. prereaction comlexes and transition states were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-9.77 -9.77 -9.39 -9.39 -7.75 -7.75 -7.68 -7.68 -7.37 -7.37 -6.68 -6.68 -6.02 -6.02 -5.30 -5.30 -4.40 -4.40 -4.10 -4.10 -3.52 -3.52 -3.40 -3.40 -3.14 -3.14 -2.18 -2.18 -2.17 -2.17 -1.90 -1.90 -1.79 -1.79 -1.36 -1.36 0.69 0.69 0.97 0.97 1.26 1.26 1.60 1.60 3.26 3.26 4.41 4.41

IRC (concatenated xyz) from TS_Ph-E and TS_Ph-Z

Binol-AlCl3 complexes

Binol is 1,1′-bi-2-naphthol

Conformational analysis of the complexes was performed with the computer program package ChemAxon Marvin (conformers plugin).
The geometries of all the conformers were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-17.08 -17.08 -15.43 -15.43 -15.39 -15.39 -15.22 -15.22 -14.93 -14.93 -14.90 -14.90 -14.79 -14.79 -13.09 -13.09 -12.00 -12.00 -9.87 -9.87 -9.52 -9.52 -8.86 -8.86 -6.49 -6.49 -6.35 -6.35 -5.78 -5.78 -5.41 -5.41 -4.76 -4.76 -4.43 -4.43 -4.43 -4.43 -4.13 -4.13 -2.01 -2.01 1.26 1.26

See also protonation of CO-tautomer

Protonated BINOL

The geometries of all the protonated forms were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

0.00 0.00 0.93 0.93 1.24 1.24 1.97 1.97 2.55 2.55 4.45 4.45 4.69 4.69 4.94 4.94 5.29 5.29 5.67 5.67 6.24 6.24 7.12 7.12 7.13 7.13 7.52 7.52 7.81 7.81 8.18 8.18 8.36 8.36 8.44 8.44 8.81 8.81 9.80 9.80 9.96 9.96 10.31 10.31 10.43 10.43 10.92 10.92 11.29 11.29 11.40 11.40 11.53 11.53 11.75 11.75 11.85 11.85 12.20 12.20 12.81 12.81 13.20 13.20 13.26 13.26 13.38 13.38 14.20 14.20 14.63 14.63 15.41 15.41 16.66 16.66 16.84 16.84 19.43 19.43 23.23 23.23 23.61 23.61 24.09 24.09 24.14 24.14 25.46 25.46 25.95 25.95 26.61 26.61 26.73 26.73 28.50 28.50

Diprotonated BINOL

The geometries of all the protonated forms were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

Yellow highlighted are structures from Chem. Eur. J. 2014, 20, 14816 (SI)
0.00 0.00 0.79 0.79 1.31 1.31 1.35 1.35 1.60 1.60 2.16 2.16 2.22 2.22 3.15 3.15 3.37 3.37 3.37 3.37 3.58 3.58 3.86 3.86 3.91 3.91 4.61 4.61 4.64 4.64 4.76 4.76 5.39 5.39 5.52 5.52 5.55 5.55 5.70 5.70 5.83 5.83 5.95 5.95 6.10 6.10 6.11 6.11 6.18 6.18 6.25 6.25 6.40 6.40 6.55 6.55 6.61 6.61 6.76 6.76 6.97 6.97 7.31 7.31 7.43 7.43 7.78 7.78 7.83 7.83 8.21 8.21 8.25 8.25 8.53 8.53 8.60 8.60 8.80 8.80 8.96 8.96 9.11 9.11 9.12 9.12 9.39 9.39 9.51 9.51 9.79 9.79 9.89 9.89 10.13 10.13 10.20 10.20 10.21 10.21 10.26 10.26 10.28 10.28 10.28 10.28 10.30 10.30 10.37 10.37 10.37 10.37 10.39 10.39 10.41 10.41 10.47 10.47 10.62 10.62 10.67 10.67 10.73 10.73 10.76 10.76 10.84 10.84 10.86 10.86 10.88 10.88 10.96 10.96 11.20 11.20 11.30 11.30 11.36 11.36 11.61 11.61 11.74 11.74 11.76 11.76 11.88 11.88 11.89 11.89 12.00 12.00 12.00 12.00 12.81 12.81 12.90 12.90 12.92 12.92 12.96 12.96 13.08 13.08 13.24 13.24 13.33 13.33 13.37 13.37 13.58 13.58 13.62 13.62 13.72 13.72 13.76 13.76 13.79 13.79 13.91 13.91 14.06 14.06 14.07 14.07 14.25 14.25 14.38 14.38 14.57 14.57 14.58 14.58 14.79 14.79 14.81 14.81 15.01 15.01 15.01 15.01 15.17 15.17 15.18 15.18 15.28 15.28 15.55 15.55 16.18 16.18 16.23 16.23 16.40 16.40 16.41 16.41 16.46 16.46 16.51 16.51 16.63 16.63 16.65 16.65 16.75 16.75 16.92 16.92 17.12 17.12 17.20 17.20 17.45 17.45 17.72 17.72 17.82 17.82 17.85 17.85 17.98 17.98 18.10 18.10 18.27 18.27 18.46 18.46 18.47 18.47 18.67 18.67 18.70 18.70 18.84 18.84 18.91 18.91 18.97 18.97 19.06 19.06 19.56 19.56 19.79 19.79 19.80 19.80 19.88 19.88 19.89 19.89 19.99 19.99 20.10 20.10 20.12 20.12 20.31 20.31 20.99 20.99 21.05 21.05 21.08 21.08 21.11 21.11 21.42 21.42 21.86 21.86 21.99 21.99 22.04 22.04 22.24 22.24 22.37 22.37 22.59 22.59 22.94 22.94 23.22 23.22 23.68 23.68 23.86 23.86 23.94 23.94 23.99 23.99 24.09 24.09 24.39 24.39 24.50 24.50 24.52 24.52 24.53 24.53 24.58 24.58 24.91 24.91 25.04 25.04 25.08 25.08 25.28 25.28 25.30 25.30 25.78 25.78 25.87 25.87 26.11 26.11 26.15 26.15 26.31 26.31 26.41 26.41 26.44 26.44 26.46 26.46 26.51 26.51 26.58 26.58 26.64 26.64 26.78 26.78 26.85 26.85 26.89 26.89 26.90 26.90 26.96 26.96 27.09 27.09 27.15 27.15 27.39 27.39 27.70 27.70 27.74 27.74 28.04 28.04 28.49 28.49 28.56 28.56 28.59 28.59 28.72 28.72 28.86 28.86 28.88 28.88 29.04 29.04 29.58 29.58 29.58 29.58 29.59 29.59 29.67 29.67 29.89 29.89 29.92 29.92 29.95 29.95 30.06 30.06 30.12 30.12 30.14 30.14 30.15 30.15 30.21 30.21 30.52 30.52 30.73 30.73 30.84 30.84 30.89 30.89 30.93 30.93 31.00 31.00 31.12 31.12 31.19 31.19 31.32 31.32 31.37 31.37 31.38 31.38 31.53 31.53 31.56 31.56 31.76 31.76 32.98 32.98 33.00 33.00 33.02 33.02 33.60 33.60 33.64 33.64 33.87 33.87 34.27 34.27 34.42 34.42 34.87 34.87 34.89 34.89 35.09 35.09 35.38 35.38 35.40 35.40 35.72 35.72 35.76 35.76 35.76 35.76 36.01 36.01 36.04 36.04 36.04 36.04 36.19 36.19 36.35 36.35 36.81 36.81 36.95 36.95 37.03 37.03 37.30 37.30 37.34 37.34 38.00 38.00 38.92 38.92 39.09 39.09 39.26 39.26 39.97 39.97 42.12 42.12 42.20 42.20 42.86 42.86 44.62 44.62 48.16 48.16 48.18 48.18 49.15 49.15 52.51 52.51 53.17 53.17


Relaxation of 247.OO into 010.88



IRC (concatenated xyz)

Protonated CO-tautomer of Binol-AlCl3 complex

Tautomers of Binol-AlCl3 complex


The geometries of all the protonated forms were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

0.00 0.00 0.12 0.12 0.17 0.17 0.32 0.32 0.57 0.57 2.02 2.02 2.12 2.12 2.16 2.16 2.20 2.20 2.46 2.46 2.72 2.72 2.85 2.85 2.90 2.90 2.97 2.97 3.16 3.16 3.23 3.23 3.35 3.35 3.88 3.88 4.03 4.03 4.18 4.18 4.83 4.83 5.04 5.04 5.05 5.05 5.16 5.16 5.42 5.42 6.04 6.04 6.19 6.19 6.89 6.89 7.38 7.38 7.55 7.55 7.61 7.61 7.82 7.82 8.41 8.41 9.85 9.85 9.96 9.96 10.01 10.01 10.06 10.06 11.08 11.08 11.35 11.35 12.24 12.24 12.34 12.34 12.82 12.82 13.29 13.29 14.20 14.20 14.26 14.26 15.02 15.02 29.41 29.41 33.02 33.02


Transition states of racemization of BINOL

The geometries of all the protonated forms and transition states were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

Energy level titles:
first digit — charge of the structure
second letter "l" — structure from Chem. Eur. J. 2014, 20, 14816 (SI) optimized by DFT/PBE/L1
suffix "TS" — transition state of racemization

 0.00 0.00 29.59 29.59 34.16 34.16 35.11 35.11 36.11 36.11 40.20 40.20 40.56 40.56 43.15 43.15 45.49 45.49 47.15 47.15 47.29 47.29 57.47 57.47 9.00 9.00 17.47 17.47 13.44 13.44 14.86 14.86 0.00 0.00 23.28 23.28 23.87 23.87 25.20 25.20 30.42 30.42 34.77 34.77 36.96 36.96 37.95 37.95 38.77 38.77 39.86 39.86 0.00 0.00 3.15 3.15 3.58 3.58 4.61 4.61 8.25 8.25 10.20 10.20 10.37 10.37 15.92 15.92 15.97 15.97 20.33 20.33 38.27 38.27 45.81 45.81 46.79 46.79

Zero energy levels: 0-00 — ZZ-BINOL, 1-00 — 01.1, 2-00 — 001.88

IRC (concatenated xyz): 0-11_b-a, 1-11_d-a (not racemization), 2l-1 (not racemization), 2-88_a

Rotations in 1,1'-diprotonated BINOLs

The geometries of all the protonated forms and transition states were optimized by DFT (Priroda program, PBE functional, L1 basis (Λ01, cc-pVDZ analog)).


On figure(s) below click on the level title to download xyz file ==>
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Correspondence with previous diagram:
11R and 11S are 008.11, 9R is 011.11, 9S is 014.11

 0.00 0.00 0.01 0.01 0.74 0.74 1.46 1.46 7.01 7.01 7.98 7.98 9.70 9.70 9.70 9.70 9.74 9.74 10.95 10.95 14.54 14.54 16.31 16.31


IRC (concatenated xyz): 11R-11S, 9R-9S