FAIR Data table. Free energies for

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FAIR Data Table. Activation energies and calculated deuterium kinetic isotope effects for Swern oxidation of benzyl alcohol ("Endo-TS1")
Solvent^{DOI: TS,React}	ΔG^‡_{298.15, kcal mol^-1}	TS S-O length, Å	ν_i, cm^-1	195.15K			210.15K			226.15K			250.15K
Solvent^{DOI: TS,React}	ΔG^‡_{298.15, kcal mol^-1}	TS S-O length, Å	ν_i, cm^-1	1° KIE	2° KIE	1°/2° KIE	1° KIE	2° KIE	1°/2° KIE	1° KIE	2° KIE	1°/2° KIE	1° KIE	2° KIE	1°/2° KIE
PM7 (Semi-Empirical Method)
Carbon tetrachloride ^TS,^R	29.609	1.799	-1630.40	33.292	1.346	24.738	11.687	1.166	10.021	6.455.659	1.115	5.791	3.264	1.076	3.033
Chlorobenzene ^TS,^R	27.547	1.791	-1605.03	23.432	1.365	17.172	9.713	1.229	7.904	5.545	1.176	4.714	2.773	1.131	2.453
Chloroform ^TS,^R	29.156	1.792	-1608.50	26.538	1.277	20.775	10.726	1.151	9.314	6.063	1.107	5.476	3.015	1.071	2.815
Dichloromethane^TS,^R	27.539	1.789	-1598.97	22.291	1.351	16.506	9.504	1.225	7.757	5.449	1.174	4.640	2.705	1.129	2.396
B3LYP/6-31+G(d,p)
Carbon tetrachloride ^TS,^R	4.891	2.263	-337.50	2.673	1.286	2.078	2.495	1.263	1.975	2.342	1.243	1.885	2.164	1.217	1.777
Chlorobenzene ^TS,^R	4.276	2.285	-299.40	2.516	1.273	1.976	2.359	1.251	1.885	2.224	1.232	1.805	2.065	1.208	1.709
Chloroform ^TS,^R	4.369	2.281	-305.76	2.542	1.275	1.994	2.382	1.253	1.901	2.244	1.234	1.819	2.082	1.210	1.721
Dichloromethane ^TS,^R	4.079	2.292	-287.04	2.463	1.268	1.942	2.314	1.247	1.855	2.184	1.229	1.778	2.032	1.205	1.686
Dichloroethane ^TS,^R	4.027	2.293	-284.25	2.452	1.267	1.935	2.304	1.246	1.848	2.176	1.228	1.772	2.025	1.205	1.681
B3LYP/Def2-SVP
Dichloromethane^TS,^R	3.631	2.248	-312.58	2.150	1.262	1.704	2.041	1.242	1.643	1.946	1.224	1.589	1.832	1.202	1.524
B3LYP/Def2-SVPP
Dichloromethane^TS,^R	3.242	2.246	-313.78	2.156	1.279	1.686	2.046	1.275	1.627	1.950	1.238	1.575	1.836	1.214	1.512
B3LYP/Def2-TZVPP
Carbon tetrachloride^TS,^R	8.732	2.267	-459.64	3.690	1.342	2.749	3.351	1.311	2.557	3.071	1.284	2.392	2.754	1.252	2.201
Chlorobenzene ^TS,^R	8.400	2.290	-421.92	3.456	1.330	2.598	3.159	1.301	2.427	2.910	1.276	2.281	2.627	1.246	2.109
Chloroform^TS,^R	8.385	2.286	-428.26	3.494	1.332	2.623	3.191	1.303	2.449	2.937	1.277	2.299	2.649	1.247	2.124
Dichloromethane^TS,^R	7.969	2.297	-409.63	3.380	1.327	2.546	3.096	1.299	2.383	2.857	1.274	2.242	2.585	1.244	2.077
Dichloroethane^TS,^R	7.834	2.299	-406.84	3.362	1.327	2.534	3.081	1.299	2.373	2.845	1.274	2.233	2.575	1.244	2.070
B3LYP/Def2-QZVPP
Carbon tetrachloride^TS,^R	9.537	2.269	-464.72	3.867	1.339	2.888	3.499	1.308	2.675	3.195	1.281	2.494	2.854	1.249	2.284
Chlorobenzene^TS,^R	8.478	2.292	-425.19	3.587	1.330	2.697	3.270	1.301	2.512	3.005	1.276	2.354	2.703	1.246	2.170
Chloroform^TS,^R	8.732	2.288	-431.85	3.633	1.332	2.727	3.307	1.303	2.538	3.036	1.278	2.377	2.729	1.247	2.188
Dichloromethane^TS,^R	7.971	2.300	-412.35	3.501	1.326	2.641	3.198	1.298	2.464	2.945	1.273	2.313	2.656	1.243	2.136
Dichloroethane^TS,^R	7.849	2.302	-409.44	3.483	1.325	2.628	3.183	1.397	2.454	2.932	1.272	2.304	2.645	1.243	2.128
B3LYP+GD3+BJ/Def2-QZVPP (endo-TS)
Dichloromethane^TS,^R	6.720	2.284	-405.65	3.288	1.266	2.598^c	3.018	1.244	2.426	2.791	1.225	2.279	2.531	1.202	2.106
Dichloromethane^TS,^R	6.720	2.284	-405.65	3.246	1.280	2.536^d	2.981	1.256	2.372	2.758	1.236	2.232	2.503	1.212	2.066
B3LYP+GD3+BJ/Def2-QZVPP (endo-TS)^e
Dichloromethane^TS,^R	7.317	2.287	-399.14	3.203	1.276	2.510^c	2.945	1.253	2.350	2.728	1.233	2.212	2.479	1.210	2.050
B3LYP+GD3+BJ/Def2-QZVPP (exo-TS)
Dichloromethane^TS,^R	6.411	2.268	-400.40	3.317	1.227	2.704^c	3.043	1.209	2.517	2.812	1.193	2.357	2.549	1.174	2.171
ωB97XD/Def2-TZVPP
Carbon tetrachloride^TS,^R	10.179	2.209	-601.52	4.464	1.420	3.144	3.927	1.368	2.871	3.515	1.327	2.648	3.080	1.283	2.400
Chlorobenzene^TS,^R	9.403	2.231	-549.34	3.878	1.394	2.782	3.482	1.352	2.576	3.165	1.317	2.403	2.818	1.277	2.206
Chloroform^TS,^R	9.540	2.227	-557.69	3.958	1.398	2.830	3.543	1.355	2.616	3.214	1.319	2.437	2.855	1.279	2.233
Dichloromethane^TS,^R	9.136	2.238	-532.74	3.734	1.385	2.696	3.369	1.345	2.505	3.074	1.312	2.343	2.748	1.274	2.157
Dichloroethane^TS,^R	9.067	2.240	-529.39	3.708	1.384	2.680	3.348	1.344	2.491	3.057	1.311	2.332	2.735	1.273	2.148
ωB97XD/Def2-QZVPP
Carbon tetrachloride^TS,^R	10.455	2.210	-605.25	4.717	1.431	3.297	4.128	1.377	2.998	3.680	1.335	2.756	3.208	1.290	2.487
Chlorobenzene^TS,^R	11.170	2.233	-551.97	4.242	1.395	3.042	3.781	1.352	2.797	3.414	1.316	2.593	3.014	1.277	2.361
Chloroform^TS,^R	9.904	2.229	-560.62	4.155	1.405	2.958	3.705	1.360	2.724	3.349	1.324	2.530	2.962	1.283	2.309
Dichloromethane^TS,^R	9.783	2.241	-535.57	4.090	1.386	2.950	3.663	1.346	2.722	3.320	1.312	2.530	2.943	1.274	2.311
Dichloroethane^TS,^R	9.686	2.243	-531.52	4.056	1.384	2.931	3.636	1.344	2.706	3.299	1.311	2.517	2.927	1.272	2.300
B2PLYP-D3/Def2-TZVPP
Carbon tetrachloride^TS,^R	5.464	2.240	-469.08	3.712	1.367	2.716	3.368	1.332	2.528	3.084	1.303	2.368	2.765	1.268	2.181
Chlorobenzene^TS,^R	4.867	2.255	-442.10	3.546	1.354	2.620	3.233	1.322	2.446	2.973	1.294	2.297	2.677	1.261	2.124
Chloroform^TS,^R	4.932	2.252	-446.48	3.571	1.356	2.633	3.253	1.324	2.458	2.989	1.296	2.307	2.691	1.262	2.132
Dichloromethane^TS,^R	6.622	2.259	-433.38	3.499	1.348	2.596	3.195	1.317	2.426	2.941	1.290	2.280	2.652	1.258	2.109
Dichloroethane^TS,^R	6.445	2.261	-432.01	3.497	1.347	2.595	3.192	1.316	2.425	2.939	1.289	2.279	2.650	1.257	2.109
B2PLYP-D3/Def2-QZVPP (endo-TS)
Dichloromethane^TS,^R	6.687	2.264	-433.62	3.586	1.295	2.770 ^c	3.268	1.269	2.574	3.002	1.247	2.407	2.701	1.221	2.213
Dichloromethane^TS,^R	6.687	2.264	-433.62	3.555	1.280	2.776 ^d	3.240	1.256	2.579	2.978	1.235	2.411	2.681	1.210	2.215
B2PLYP-D3/Def2-QZVPP (exo-TS)
Dichloromethane^TS,^R	6.235	2.248	-427.67	3.604	1.254	2.874(2.824)^b	3.283	1.233	2.664	3.016	1.214	2.485	2.713	1.192	2.276 (2.245)^b
B3LYP/Def2-TZVPP + explicit 1CHCl₃
Chloroform^TS,^R	4.665	2.349	-381.45	3.085	1.313	2.349	2.846	1.287	2.212	2.645	1.264	2.093	2.412	1.235	1.953
B3LYP+GD3+BJ/Def2-TZVPP + explicit 1CHCl₃
Chloroform^TS,^R	5.483	2.309	-351.08	2.710	1.332	2.049	2.526	1.296	1.949	2.369	1.276	1.862	2.186	1.244	1.758
B3LYP+GD3+BJ/Def2-QZVPP; + explicit 1CHCl₃
Chloroform^TS,^R	5.613	2.311	-353.89	2.803	1.326	2.114	2.606	1.299	2.006	2.489	1.275	1.912	2.244	1.246	1.800
B3LYP+GD3+BJ/Def2-TZVPP; R=NMe₂
Dichloromethane^TS,^R	6.281	3.364	-716.29	8.895	1.147	7.757	6.882	1.105	6.229	5.676	1.082	5.246	4.595	1.063	4.332
B3LYP+GD3+BJ/Def2-QZVPP; R=NMe₂
Dichloromethane^TS,^R	6.436	3.3710	-764.53	12.415	1.235	10.055	8.475	1.147	7.389	6.615	1.109	5.965	5.145	1.081	4.760
B3LYP+GD3+BJ/Def2-QZVPP; R=OMe
Dichloromethane^TS,^R	6.767	3.033	-355.01	2.367	1.111	2.129	2.230	1.105	2.019	2.112	1.099	1.922	1.975	1.093	1.807
B3LYP/Def2-TZVPP; R=CF₃
Chloroform^TS,^R	21.140	2.225	-608.37	6.519	1.429	4.563	5.553	1.376	4.036	4.834	1.335	3.622	4.094	1.290	3.174
Dichloromethane^TS,^R	21.070	2.229	-607.28	6.525	1.435	4.547	5.559	1.382	4.023	4.840	1.340	3.612	4.098	1.294	3.166
B3LYP+GD3+BJ/Def2-TZVPP; R=CF₃
Dichloromethane^TS,^R	18.867	2.216	-559.79	5.264	1.437	3.661	4.611	1.389	3.320	4.102	1.350	3.039	3.555	1.305	2.724
B3LYP+GD3+BJ/Def2-QZVPP; R=CF₃
Dichloromethane^TS,^R	19.765	2.217	-569.05	5.573	1.447	3.851	4.854	1.397	3.476	4.297	1.356	3.170	3.704	1.310	2.828
B3LYP+GD3+BJ/Def2-QZVPP; R=NO₂
Dichloromethane^TS,^R	27.230	2.207	-668.78	7.039	1.593	4.420	5.840	1.502	3.889	5.010	1.437	3.486	4.194	1.371	3.059
^aCalculations at the level and solvent indicated. Data repository collection DOI: 10.14469/hpc/13058 for full details of calculations. This table has DOI: 10.14469/hpc/13105. Click on ν_i hyperlink to load 3D interactive model. ^bCombing endo-TS and exo-TS values using eqn. 1 ^cUsing rotamer 1 ("exo-derived") for reactant. ^dUsing rotamer 2 ("endo-derived") for reactant. ^eCPCM solvent model