Supplementary Information. for. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols
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1 Supplementary Information for Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols Peter Fristrup,* Matyas Tursky and Robert Madsen* Department of Chemistry, Building 21 Technical University of Denmark DK-28 Kgs. Lyngby, Denmark Table of Contents GC retention times... 2 Competition experiments... 4 Primary KIE determination... 2 Primary KIE determination with GC-FID and GC-MS measurements Racemisation experiment Validation of computational method using two available X-ray structures XYZ coordinates and energies from computational study Calculation of theoretical KIE IRC scan calculations of representative TS s Dihedral scan, cis-imine to trans-imine
2 GC retention times Injector temperature 3 C, detector temperature 35 C. Table A. Programmed oven temperature: start 1 C, ramp 2 C/min to 3 C, 5 3 C. Compound aniline benzyl alcohol 1,2,4,5-tetramethylbenzene naphthalene p-anisalcohol Retention Time 1.52 min 1.7 min 2.11 min 2.47 min 2.92 min Table B. Programmed oven temperature: start 1 C, ramp 2 C/min to 2 C, 5 2 C, ramp 2 C/min to 3 C, 5 3 C. Compound p-toluidine p-(trifluoromethyl)aniline p-(trifluoromethyl)benzyl alcohol p-methylbenzyl alcohol p-chloroaniline p-anisidine p-chlorobenzyl alcohol p-(dimethylamino)aniline p-(hydroxymethyl)benzonitrile p-aminobenzonitrile p-(dimethylamino)benzyl alcohol methyl p-(hydroxymethyl)benzoate methyl p-aminobenzoate p-nitrobenzyl alcohol Retention Time 1.84 min 1.85 min 1.91 min 2.14 min 2.43 min 2.51 min 2.64 min 3.31 min 3.52 min 3.76 min 3.98 min 4.8 min 4.18 min 4.21 min 2
3 Table C. Programmed oven temperature: start 1 C, ramp 5 C/min to 13 C, 2 C/min to 2 C, 5 2 C, ramp 2 C to 3 C, 5 3 C. Compound aniline benzyl alcohol 1,2,4,5-tetramethylbenzene naphthalene p-chloroaniline p-aminobenzonitrile Retention Time 1.73 min 2.5 min 2.85 min 3.53 min 3.39 min 6.72 min 3
4 OMe Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 1, p-methoxybenzyl alcohol vs. benzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-methoxybenzyl alcohol (125 μl, 1 mmol) naphthalene (129 mg, 1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion Time PhNH 2 BnOH p-meo-bnoh Naphthalene PhNH 2 BnOH p-meo-bnoh - no cat cat min h h h h h h h y = x R 2 = H 4
5 Me Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 2, p-methylbenzyl alcohol vs. benzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-methylbenzyl alcohol (122 mg, 1 mmol) naphthalene (126 mg, 1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time PhNH2 BnOH p-me-bnoh Naphthalene PhNH2 BnOH p-me-bnoh - no cat cat min h h h h h h h h y = 1.669x R 2 = H 5
6 CF3 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 3, p-(trifluoromethyl)benzyl alcohol vs. benzyl alcohol K 2 CO 3 (15 mg,.11 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-(trifluoromethyl)benzyl alcohol (135 μl,.99 mmol) naphthalene (127 mg, 1 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time PhNH 2 BnOH p-cf 3-BnOH Naphthalene PhNH 2 BnOH p-cf 3-BnOH - no cat cat min h h h h h h y =.1952x R 2 = H 6
7 Cl Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 4, p-chlorobenzyl alcohol vs. benzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-chlorobenzyl alcohol (143 mg, 1 mmol) naphthalene (128 mg, 1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time PhNH2 BnOH p-cl-bnoh Naphthalene PhNH2 BnOH p-cl-bnoh - no cat cat min h h h h h h y =.768x R 2 = H 7
8 COOMe Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 5, methyl p-(hydroxymethyl)benzoate vs. benzyl alcohol K 2 CO 3 (15 mg,.11 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) methyl p-(hydroxymethyl)benzoate (165 mg,.99 mmol) naphthalene (128 mg, 1 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time PhNH2 BnOH p-coome-bnoh Naphthalene PhNH2 BnOH p-coome-bnoh - no cat cat min h h h h h h h h y =.4381x R 2 = H 8
9 CN Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 6, p-(hydroxymethyl)benzonitrile vs. benzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-(hydroxymethyl)benzonitrile (132 mg,.99 mmol) naphthalene (127 mg, 1 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time PhNH 2 BnOH p-cn-bnoh Naphthalene PhNH 2 BnOH p-cn-bnoh - no cat cat min h h h h h h h h y =.2682x R 2 = H 9
10 Me2N Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Competition experiment 7, p-(dimethylamino)benzyl alcohol vs. benzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-(dimethylamino)benzyl alcohol (156 mg, 1.3 mmol) naphthalene (126 mg, 1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time PhNH 2 BnOH p-nme 2-BnOH Naphthalene PhNH 2 BnOH p-nme 2-BnOH - no cat cat min h h h h h h h y = x R 2 = H 1
11 Competition experiment 8, p-nitrobenzyl alcohol vs. p-chlorobenzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (18 μl, 2 mmol) p-chlorobenzyl alcohol (144 mg, 1.1 mmol) p-nitrobenzyl alcohol (154 mg, 1.2 mmol) naphthalene (13 mg, 1.1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time aniline p-cl-bnoh p-no 2-BnOH Naphthalene PhNH 2 p-cl-bnoh p-no 2-BnOH - no cat cat min h h h h h h y =.2943x R 2 =
12 Competition experiment 9, p-toluidine vs. aniline K 2 CO 3 (15 mg,.11 mmol) aniline (9 μl, 1 mmol) p-toluidine (17 mg, 1. mmol) benzyl alcohol (21 μl, 2.3 mmol) naphthalene (126 mg,.98 mmol) [Cp*IrCl 2 ] 2 (41 mg,.51 mmol) Areas Conversion time BnOH p-h-aniline p-me-aniline Naphthalene BnOH p-h-aniline p-me-aniline - no cat cat min h h h h h h h y = x R 2 =
13 Competition experiment 1, p-anisidine vs. aniline K 2 CO 3 (14 mg,.1 mmol) aniline (9 μl, 1 mmol) p-anisidine (122 mg,.99 mmol) benzyl alcohol (21 μl, 2.3 mmol) naphthalene (126 mg,.98 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time BnOH p-h-aniline p-meo-aniline Naphthalene BnOH p-h-aniline p-meo-aniline - no cat cat min h h h h h h h y = x R 2 =
14 Competition experiment 11, p-(trifluoromethyl)aniline vs. aniline K 2 CO 3 (14 mg,.1 mmol) aniline (9 μl, 1 mmol) p-(trifluoromethyl)aniline (125 μl, 1. mmol) benzyl alcohol (21 μl, 2.3 mmol) naphthalene (126 mg,.98 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time BnOH p-h-aniline p-cf 3-aniline Naphthalene BnOH p-h-aniline p-cf 3-aniline - no cat cat min h h h h h h h y =.665x R 2 =
15 Competition experiment 12, p-chloroaniline vs. aniline K 2 CO 3 (14 mg,.1 mmol) aniline (9 μl, 1 mmol) p-chloroaniline (129 mg, 1.1 mmol) benzyl alcohol (21 μl, 2.3 mmol) 1,2,4,5-tetramethylbenzene (126 mg,.94 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time BnOH p-h-aniline p-cl-aniline Tetramethylbenzene BnOH p-h-aniline p-cl-aniline - no cat cat min h h h h h h h y =.4431x R 2 =
16 Competition experiment 13, methyl p-aminobenzoate vs. aniline K 2 CO 3 (15 mg,.11 mmol) aniline (9 μl, 1 mmol) methyl p-aminobenzoate (152 mg, 1. mmol) benzyl alcohol (21 μl, 2.3 mmol) naphthalene (125 mg,.98 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion time BnOH p-h-aniline p-coome-aniline Naphthalene BnOH p-h-aniline p-coome-aniline - no cat cat min h h h h h h h h y =.2245x R 2 =
17 Competition experiment 14, p-aminobenzonitrile vs. p-chloroaniline K 2 CO 3 (14 mg,.1 mmol) p-chloroaniline (124 mg,.97 mmol) p-aminobenzonitrile (119 mg, 1. mmol) benzyl alcohol (21 μl, 2.3 mmol) 1,2,4,5-tetramethylbenzene (132 mg,.98 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time BnOH p-cl-aniline p-cn-aniline Tetramethylbenzene BnOH p-cl-aniline p-cn-aniline - no cat cat min h h h h h h h h y =.128x R 2 =
18 Competition experiment 15, p-(dimethylamino)aniline vs. p-anisidine K 2 CO 3 (14 mg,.1 mmol) p-anisidine (122 mg,.99 mmol) p-(dimethylamino)aniline (135 mg,.99 mmol) benzyl alcohol (21 μl, 2.3 mmol) 1,2,4,5-tetramethylbenzene (132 mg,.98 mmol) [Cp*IrCl 2 ] 2 (39 mg,.49 mmol) Areas Conversion time BnOH p-meo-aniline p-nme 2-aniline Tetramethylbenzene BnOH p-meo-aniline p-nme 2-aniline - no cat cat min min min h min min min h min h h h h
19 2.5 2 y = 5.45x R 2 =
20 d2-bnoh Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Primary KIE determination Compounds loads: K 2 CO 3 (15 mg,.11 mmol) aniline (18 μl, 2 mmol) benzyl alcohol (15 μl, 1 mmol) p-methoxybenzyl alcohol (125 μl, 1 mmol) naphthalene (125 mg,.98 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol).6.5 y =.273x R 2 = OMe k D /k OMe =.27 k OMe /k H =1.944 k H / k D =
21 Primary KIE determination with benzyl alcohol, -d 2 vs. p-chlorobenzyl alcohol K 2 CO 3 (14 mg,.1 mmol) aniline (186 mg, 2 mmol) benzyl alcohol, -d 2 (11 mg, 1 mmol) p-chlorobenzyl alcohol (142 mg, 1 mmol) naphthalene (129 mg, 1 mmol) [Cp*IrCl 2 ] 2 (4 mg,.5 mmol) Areas Conversion Time d2-bnoh p-cl-bnoh Naphthalene d2-bnoh p-cl-bnoh - no cat min h h h h h h y = 1.755x R² =
22 There seems to be a slight curvature which may arise from loss of deuterium from benzyl alcohol, -d 2. When only the first part of the curve is plotted the difference in reactivity is significantly higher (1.37)..7.6 y = x R² = Using these data one can again determine the kinetic isotope effect (KIE) as follows: k Cl /k D = 1.37 k Cl /k H =.71 k H / k D =
23 GC-MS data from primary KIE determination, benzyl alcohol, -d 2 vs. p-chlorobenzyl alcohol m/z=17 m/z=18 m/z=19 m/z=11 m/z= GC-MS data showing that the benzyl alcohol, -d 2 (m/z=11) loses its deuterium content during the reaction m/z=14 m/z=141 m/z=142 m/z=143 m/z=144 m/z= GC-MS data showing that the undeuterated p-chlorobenzyl alcohol (m/z=142) increases its deuterium content during the reaction (m/z=144). 23
24 m/z=181 m/z=182 m/z=183 m/z=184 m/z=185 m/z= GC-MS data showing the data for the unsubstituted product. Here, the deuterium content is high (m/z=184) and also remains relatively high during the reaction which illustrates that the final reduction to the amine is virtually irreversible m/z=216 m/z=217 m/z=218 m/z=219 m/z= GC-MS data for the chloro-substituted amine product. Here, the deuterium content is low in the beginning (m/z=217), but gradually increases (m/z=218). 24
25 To estimate the degree of reversibility of the initial alcohol oxidation we decided to plot the conversion of benzyl alcohol measured by GC-FID (i.e. total amount irrespective of deuterium content) versus the decrease of the m/z=11 signal benzyl alcohol (GC-FID) m/z= Since the experiment was run under competetion conditions one will not obtain absolute kinetics or reaction orders, but it is still clear that the disappearance of the benzyl alcohol is faster than the deuterium exchange of the unreacted benzyl alcohol, -d 2. The same type of analysis was carried out for p-chlorobenzyl alcohol m/z=142 p-cl-benzyl alcohol Also here the disappearance of the total amount of p-chlorobenzyl alcohol is significantly faster than the proton/deuterium exchange. 25
26 Racemisation experiment In an oven-dried Schlenk tube were placed K 2 CO 3 (4 mg,.3 mmol), (R)-1-deutero-1- phenylethanol (29 mg,.24 mmol, 81% ee), acetophenone (3 mg,.24 mmol) and dry toluene (.5 ml). The mixture was placed in an oil bath preheated to 11 C and a GC sample was taken out. Then, [Cp*IrCl 2 ] 2 (1 mg,.125 mmol) was added. After addition of the catalyst, a GC sample was taken out immediately. Then, GC samples were taken out after 3 min, 1h, 2h, 3h, 4h, 5h. At that time, GC analysis showed 8% ee (Column: Chrompack CP Chirasil-Dex CB.25 mm x 25 m column), the reaction mixture was cooled down to rt and subjected to column chromatography (hexane/et 2 O 4/1), which yielded 1 mg of 1-phenylethanol. The 1 H content was determined by NMR to be 6%. 26
27 Computational study The description of the computational method is included in the main text of the manuscript. Two available crystal structures (Refcode: DCPMIR, ARADAY1) 1 were used to access the accuracy of the applied computational method (B3LYP in combination with an effective core potential for iridium). Below is shown an overlay of the crystal structure (blue) with the calculated structure (red) (figure S1 and S2). The superimposition was performed for atoms heavier than hydrogen to avoid the otherwise dominating influence of the methyl rotation. For the DCPMIR structure the RMSD was.951 Å, indicating an acceptable overall structural similarity. The largest errors in the computational structure was found to be overly long Ir-Cl and Ir-Cpstar bonds, in both cases on the order of.4-.5å which we are confident will not influence the overall conclusions reached in this study. For ARADAY1 structure the RMSD was calculated to.1112 Å, slightly higher than for the DCPMIR structure, which to some degree can be assigned to the lack of symmetry in the crystal structure, resulting in three slightly different experimental Ir-Cl bond lengths. Figure S1 Overlay of X-ray structure (blue, DCPMIR) with a structure energy minimized using DFT/B3LYP (red). RMSD for non-hydrogen atoms were.951 Å. Figure S2 Overlay of X-ray structure (blue, ARADAY1) with a structure energy minimized using DFT/B3LYP (red). RMSD for non-hydrogen atoms were.1112 Å. (1) (a) DCPMIR: M. R. Churchill, S. A. Julis, Inorg. Chem., 1977, 16, ; (b) ARADAY1: M. Maekawa, Y. Suenaga, T. Kuroda-Sowa, M. Munakata, Anal. Sci., 24, 2, x11-x12. 27
28 XYZ Coordinates and energies for calculated complexes. Ir2_Cpstar2_Cl4_dimer E_scf (B3LYP/6-31G*) = a.u. E_scf (M6/6-31G*) = a.u. E_Gibbs = a.u. E_solv = a.u. ZPE = kcal/mol Ir Cl Cl C C C C C C C C C C Cl Ir Cl C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H
29 Ir_Cpstar_Cl2_monomer E_scf (B3LYP/6-31G*) = a.u. E_scf (M6/6-31G*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol Ir Cl Cl C C C C C C H H H C H H H C H H H C H H H C H H H Ir_Cpstar_PhNH2_PhCO_alcohol (1a) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C... C C C C C H H H C H H H C H H H C H
30 H H C H H H H Ir C O H C C C C C C H H H H H N H H C C C C C C H H H H H Ir_Cpstar_PhNH2_PhCO_E_TS (1b) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C... C C C C C H H H C H H H C H H H C H H
31 H C H H H H Ir C O H C C C C C C H H H H H N H H C C C C C C H H H H H Ir_Cpstar_PhNH2_PhCO_aldehyde (1c) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C... C C C C C H H H C H H H C H H H C H H H
32 C H H H H Ir C O H C C C C C C H H H H H N H H C C C C C C H H H H H Ir_Cpstar_H_Hemiaminal_bidentate (1d) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C O H H N C C C C C C H H H H H C C C C C
33 C H H H H H H Ir C C C C C C H H H C H H H C H H H C H H H C H H H H Ir_Cpstar_H_Hemiaminal_Hshift (1e) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C O H H N C C C C C C H H H H H C C C C
34 C C H H H H H Ir C C C C C C H H H C H H H C H H H C H H H C H H H H H Ir_Cpstar_PhNH2_PhCNPh_imine (1f) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C... C C C C C H H H C H H H C H H H C H H H
35 C H H H H Ir C N H C C C C C C H H H H H C C C C C C H H H H H N H H C C C C C C H H H H H Ir_Cpstar_PhNH2_PhCNPh_E_TS (1g) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol C... C C C C C H H H C
36 H H H C H H H C H H H C H H H H Ir C N H C C C C C C H H H H H C C C C C C H H H H H N H H C C C C C C H H H H H Ir_Cpstar_PhNH2_PhCNPh_amine (1h) E_scf (B3LYP/6-31G*) = a.u. E_scf (B3LYP/6-31G+*) = a.u. E_scf (M6/6-31G*) = a.u. E_scf (M6/6-31G+*) = a.u. E_solv = a.u. E_Gibbs = a.u. ZPE = kcal/mol 36
37 C... C C C C C H H H C H H H C H H H C H H H C H H H H Ir C N H C C C C C C H H H H H C C C C C C H H H H H N H H C C C C C C H H H H H
38 38
39 Calculation of theoretical KIE The calculation of the theoretical KIE was performed using the Hessian calculated in gas phase for the complexes 1a and 1b. To allow comparison with experimental results the Gibbs free energy was evaluated at T=383 K (=11 C, bp. of toluene). This gave the following results: Ir_Cpstar_PhNH2_PhCO_E_TS_freq_D_383K Ir_Cpstar_PhNH2_PhCO_E_TS_alcohol_min_full_freq_D_383K Ir_Cpstar_PhNH2_PhCO_E_TS_freq_H_383K Ir_Cpstar_PhNH2_PhCO_E_TS_alcohol_min_full_freq_H_383K a.u a.u a.u a.u. From this we find an activation energy of 37.7 kj/mol (proton) and 4.9 kj/mol (deuterium). This difference in energy of 3.2 kj/mol corresponds to a difference in reaction rate of 2.7 when using a Boltzmann expression evaluated at T=383K. Performing a similar analysis using differences in zero-point energies (ZPE) resulted in a calculated KIE of 2.73, thus documenting that the observed effect arises mainly from differences in bond strengths, as expected. 39
40 IRC scan calculations An IRC scan calculations was carried out for a representative beta-hydride elimination. Below are shown three structures, one close to the TS and one from either end of the IRC scan. Figure 1 IRC step close to TS (forward1) Figure 2 IRC step close to alcohol (reverse 8) 4
41 Figure 3 IRC step close to aldehyde (forward 1) Table 1 Data from the IRC scan of a representative beta-hydride abstraction Ir_Cpstar_PhNH2_PhCO_Z_TS_freq_IRC point # Rxn. Coord Energy (Hartree) Relative Energy (kj/mol) C-H distance (Å)
42 Figure 4 Relative energy vs. IRC coordinate for beta-hydride elimination Figure 5 Relative energy vs. C-H distance (Å) for the C-H bond which is being broken/formed. 42
43 An IRC scan calculations was also carried out for a representative imine reduction. Below are shown three structures, one close to the TS and one from either end of the IRC scan. Figure 6 IRC step close to TS (forward1) Figure 7 IRC step close to amine (reverse 1) 43
44 Figure 8 IRC step close to imine (forward 1) Table 2 Data from the IRC scan of a representative imine reduction. Ir_Cpstar_PhNH2_PhCNPh_E_TS_freq_IRC point # Rxn. Coord Energy Relative Energy (kj/mol) C-H distance (Å)
45 Figure 9 Relative energy vs. IRC coordinate for imine reduction. Figure 1 Relative energy vs. C-H distance (Å) for the C-H bond which is being broken/formed. 45
46 Dihedral scan, cis-imine to trans-imine To estimate the possibility of cis to trans isomerization of the intermediate imine, a dihedral scan calculation was carried out (B3LYP/6-31G*, gas phase). It is clear that the barrier is very high, which can be ascribed to the very strong electrostatic interaction between the hydride and the proton on the phenyl group of the imine. Figure 11 Energy profile for the dihedral scan. Table 3 The data obtained from the dihedral scan. dihedral angle Energy (Ha) Relative Energy Below are shown the structures obtained during the scan from cis-imine to trans-imine: 46
47 Figure 12 Structures obtained in the dihedral scan from cis-imine (top-left) to trans-imine (bottom right). 47
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