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76849107746
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The distance between the silicon and the oxygen in DMF has been calculated to be 3187 Å at the MP2/6-31+G level of theory
-
The distance between the silicon and the oxygen in DMF has been calculated to be 3187 Å at the MP2/6-31+G level of theory.
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60
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76849100742
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note
-
In the case of formaldehyde, there appears another transition state between TS2 and R2 in which the aldehyde molecule has a strongly pyramidized structure. It may not be essential to the allylation reaction. See the Supporting Information.
-
-
-
-
63
-
-
76849104841
-
-
Estimated by the energy difference between TS3 and (the DMFcoordinated allylsilane + benzaldehyde) frozen to the structures in TS3
-
Estimated by the energy difference between TS3 and (the DMFcoordinated allylsilane + benzaldehyde) frozen to the structures in TS3.
-
-
-
-
64
-
-
76849092400
-
-
The energy difference between TS3 and (the benzaldehydecoordinated allylsilane + DMF)
-
The energy difference between TS3 and (the benzaldehydecoordinated allylsilane + DMF).
-
-
-
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67
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38149037245
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Denmark, S.E.1
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65349192848
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The experimental and theoretical study performed by Hrdina et al. indicated that the allylation reaction of aldehydes catalyzed by bipyridine N, N'-dioxides proceeds via two different reaction mechanisms depending on the solvent. See: Hrdina, R.; Opekar, F.; Roithová, J.; Kotora, M. Chem. Commun. 2009, 2314-2316.
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76849116652
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note
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The bonding contribution of the s-type orbitais in electron derealization is counterbalanced by their antibonding participation in the overlap repulsion between the occupied MOs of the two fragments, and therefore, the s-type orbital functions of Si do not participate in the Si-O(benzaldehyde) bond both at TS1 and at TS3.
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73
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53549112555
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A recent DFT study of the octahedral complex of dichlorosilane with substituted pyridines suggested the strongly polar Si-Cl bonds. See: Fester, G. W.; Wagler, J.; Brendler, E.; Böhme, U.; Roewer, G.; Kroke, E. Chem. Eur. J. 2008, 14, 3164-3176.
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76849093999
-
-
note
-
a bond not only in TS1 but also in TS3.
-
-
-
-
79
-
-
76849115052
-
-
1 on the Si center has been found to be 79%, the same magnitude as that in TS3
-
1 on the Si center has been found to be 79%, the same magnitude as that in TS3.
-
-
-
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80
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0031209054
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76849101103
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note
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nonel is the sum of the cavitation, dispersion, and repulsion energies in the SCRF calculations. The united atom, topological model applied to radii optimized at the RHF/6-31G level of theory (UAHF) was utilized for the PCM calculations.
-
-
-
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