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Ananikov, V.P.1
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Morokuma, K.3
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94
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79957726092
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note
-
With such a difference in the activation barriers, the direct product of acetylene insertion into the M-P bond should be higher in energy compared to complex III, if additional stabilization by coordination of the oxygen atom would not be present. This will be shown later with the substrate, where such additional coordination is not possible.
-
-
-
-
95
-
-
79957685787
-
-
note
-
For clarity reasons insertion into the M-H bond is omitted in Figure 1 b and 1 c, as the representations of the structures do not differ significantly from those shown in Figure 1 a. Geometry data for all studied reactions are provided in Table 2.
-
-
-
-
96
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79957763219
-
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See Figure S1 in the Supporting Information for the structures involved in the Rh system. A similar nature of the transition states was found, but with the difference that Rh complexes adopted a pyramidal geometry arrangement, while Pd, Ni, and Pt complexes possessed square-planar or T-shaped geometries
-
See Figure S1 in the Supporting Information for the structures involved in the Rh system. A similar nature of the transition states was found, but with the difference that Rh complexes adopted a pyramidal geometry arrangement, while Pd, Ni, and Pt complexes possessed square-planar or T-shaped geometries.
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-
-
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97
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79957717353
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note
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2=CH->σ-CH(P)=CH-≤laquo;π-HC≡CH (where P is a phosphorus group).
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-
-
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98
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79957777609
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The same orientation of the P=O group in these transition states was employed for comparison
-
The same orientation of the P=O group in these transition states was employed for comparison.
-
-
-
-
99
-
-
79957669819
-
-
note
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2 group, but this was not addressed in the present study. For comparison, a similar procedure to optimize the structures of products was utilized for all complexes.
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-
-
-
100
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79957778834
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Either direct isomerization or a dissociative mechanism (i.e. alkyne dissociation, isomerization of T-shaped [M(H)(P)(L)] species, and alkyne recoordination) can be involved
-
Either direct isomerization or a dissociative mechanism (i.e. alkyne dissociation, isomerization of T-shaped [M(H)(P)(L)] species, and alkyne recoordination) can be involved.
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-
-
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101
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79957750602
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In fact, metal hydrides may be destroyed in the presence of acids (even catalytic amounts of acid) and this procedure was utilized to control the regioselectivity of the reaction (see Refs. [8, 9])
-
In fact, metal hydrides may be destroyed in the presence of acids (even catalytic amounts of acid) and this procedure was utilized to control the regioselectivity of the reaction (see Refs. [8, 9]).
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102
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26844534384
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114
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79957773678
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-1 for the transition states corresponding to acetylene insertion into the M-H bond (IV-TS and X-TS).
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117
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