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• W2023360007 endingPage "15634" @default.
• W2023360007 startingPage "15625" @default.
• W2023360007 abstract "Abstract The CH activation in the tandem, “merry‐go‐round”, [(dppp)Rh]‐catalyzed (dppp=1,3‐bis(diphenylphosphino)propane), four‐fold addition of norborene to PhB(OH) 2 has been postulated to occur by a C(alkyl)H oxidative addition to square‐pyramidal Rh III H species, which in turn undergoes a C(aryl)H reductive elimination. Our DFT calculations confirm the Rh I /Rh III mechanism. At the IEFPCM(toluene, 373.15 K)/PBE0/DGDZVP level of theory, the oxidative addition barrier was calculated to be 12.9 kcal mol −1 , and that of reductive elimination was 5.0 kcal mol −1 . The observed selectivity of the reaction correlates well with the relative energy barriers of the cycle steps. The higher barrier (20.9 kcal mol −1 ) for norbornyl–Rh protonation ensures that the reaction is steered towards the 1,4‐shift (total barrier of 16.3 kcal mol −1 ), acting as an equilibration shuttle. The carborhodation (13.2 kcal mol −1 ) proceeds through a lower barrier than the protonation (16.7 kcal mol −1 ) of the rearranged aryl–Rh species in the absence of o ‐ or m ‐substituents, ensuring multiple carborhodations take place. However, for 2,5‐dimethylphenyl, which was used as a model substrate, the barrier for carborhodation is increased to 19.4 kcal mol −1 , explaining the observed termination of the reaction at 1,2,3,4‐tetra( exo ‐norborn‐2‐yl)benzene. Finally, calculations with ( Z )‐2‐butene gave a carborhodation barrier of 20.2 kcal mol −1 , suggesting that carborhodation of non‐strained, open‐chain substrates would be disfavored relative to protonation." @default.
• W2023360007 created "2016-06-24" @default.
• W2023360007 creator A5003289867 @default.
• W2023360007 creator A5017316054 @default.
• W2023360007 creator A5018756920 @default.
• W2023360007 creator A5055900883 @default.
• W2023360007 creator A5082770970 @default.
• W2023360007 date "2014-09-26" @default.
• W2023360007 modified "2023-10-18" @default.
• W2023360007 title "First Principles (DFT) Characterization of Rh^I/dppp-Catalyzed CH Activation by Tandem 1,2-Addition/1,4-Rh Shift Reactions of Norbornene to Phenylboronic Acid" @default.
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