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This is based on experience gained from previous studies (see reference [13c-e,14b-d,15c]), which indicated that the reliability of the assessed free-energy landscape of processes as mechanistically diverse as the one studied herein critically relies on a computational protocol that accounts adequately for electronic and steric factors and also major environmental effects (see computational methodology)
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This is based on experience gained from previous studies (see reference [13c-e,14b-d,15c]), which indicated that the reliability of the assessed free-energy landscape of processes as mechanistically diverse as the one studied herein critically relies on a computational protocol that accounts adequately for electronic and steric factors and also major environmental effects (see computational methodology).
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77949314126
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77949315838
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ISO[4] (see Figure 4)
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ISO[4] (see Figure 4).
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147
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77949320806
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Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpic barrier
-
Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpic barrier.
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77949325378
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Total energetics is given relative to the 3t-S catalyst resting state
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Total energetics is given relative to the 3t-S catalyst resting state.
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-
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150
-
-
77949312497
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-1 between rival cyclisation and protonolysis steps leads one to conclude with some confidence that protonolysis is turnover limiting
-
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-
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-
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152
-
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77949322964
-
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2) would enhance the observed rate
-
2) would enhance the observed rate.
-
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153
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77949333491
-
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≠) can be estimated for the IHC of 17t by 2
-
≠) can be estimated for the IHC of 17t by 2.
-
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154
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-
77949320050
-
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-1 between, isomerisa- tion and protonolysis steps is smaller than the error margin of the employed DFT method, if chemically distinct elementary processes are concerned
-
-1 between, isomerisa- tion and protonolysis steps is smaller than the error margin of the employed DFT method, if chemically distinct elementary processes are concerned.
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77949312995
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The free energy gap is given relative to parent (CGC)Th compounds with a N-tBu group
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The free energy gap is given relative to parent (CGC)Th compounds with a N-tBu group.
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The participation of the 4f-shell in binding has been probed by employing a 4f-in-valence pseudopotential for Sm, but found being negligibly small. See the Supporting Information for further details
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