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At the B3LYP/lan2ldz level of theory see Computational Study for details
-
At the B3LYP/lan2ldz level of theory (see Computational Study for details).
-
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42
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67849095543
-
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The same result was obtained when 2a and 2h were used. Here three doublets were observed, (6 25.8, J(Rh-P) = 192 Hz; δ 22.1, J(Rh- P) = 191 Hz; δ 21.9, J(Rh-P) = 190 Hz); however, the two upheld doublets are present when only 2h is added, and thus are likely two binding modes of 2h.
-
The same result was obtained when 2a and 2h were used. Here three doublets were observed, (6 25.8, J(Rh-P) = 192 Hz; δ 22.1, J(Rh- P) = 191 Hz; δ 21.9, J(Rh-P) = 190 Hz); however, the two upheld doublets are present when only 2h is added, and thus are likely two binding modes of 2h.
-
-
-
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43
-
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67849118926
-
-
At 0 °C, a small amount 3, of an unidentified species was observed in the 31P NMR spectrum
-
31P NMR spectrum.
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Three-coordinate Rh(I) have been reported in the literature: (a) Yared, Y. W.; Miles, S. L.; Bau, R.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 7067.
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It is also possible that reversible insertion steps could lead to a pre- equilibrium isotope effect which would translate to different rates of rate-limiting reductive elimination based on different concentrations of the intermediate prior to reductive elimination. However, we believe this is unlikely since the observed κH/κ D, 1.8 is large for a thermodynamic isotope effect:(a) Kogut, E, Zeller, A, Warren, T. H, Strassner, T. J. Am. Chem. Soc. 2004, 126, 11984 Also see Computational Study for additional support for ketone insertion as the rate- determining step
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D = 1.8 is large for a thermodynamic isotope effect:(a) Kogut, E.; Zeller, A.; Warren, T. H.; Strassner, T. J. Am. Chem. Soc. 2004, 126, 11984 Also see Computational Study for additional support for ketone insertion as the rate- determining step.
-
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-
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51
-
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67849086981
-
-
D = 3.3 ± 0.3 was determined for the same substrate with [Rh(R)-DTBM-SEGPHOS](BF4).
-
D = 3.3 ± 0.3 was determined for the same substrate with [Rh(R)-DTBM-SEGPHOS](BF4).
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67849085142
-
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Of note, when the tBu-substituted ketone 1k was added (20 equiv) to a solution of Rh((R)-DTBM-SEGPHOS)]BF4 in CD2Cl 2, the spectrum showed only one doublet δ 39.1, J, 201 Hz, We believe the steric bulk of the tBu group prevents coordination of a second equivalent of substrate
-
2, the spectrum showed only one doublet (δ 39.1, J = 201 Hz). We believe the steric bulk of the tBu group prevents coordination of a second equivalent of substrate.
-
-
-
-
54
-
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67849088847
-
-
See Supporting Information for a discussion of how Keq can be estimated by two complementary methods
-
See Supporting Information for a discussion of how Keq can be estimated by two complementary methods.
-
-
-
-
55
-
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67849086982
-
-
See Supporting Information for a rate law describing substrate and product dependences
-
See Supporting Information for a rate law describing substrate and product dependences.
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Substrate 1t was inadvertantly synthesized via a Swern oxidation of the keto-alcohol precursor of 1s. See Supporting Information for details.
-
Substrate 1t was inadvertantly synthesized via a Swern oxidation of the keto-alcohol precursor of 1s. See Supporting Information for details.
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