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- W2328066145 endingPage "512" @default.
- W2328066145 startingPage "505" @default.
- W2328066145 abstract "The room-temperature reaction between the Rh(I) precursor [Rh(COE)2(acetone)2]BF4 (COE = cyclooctene) and a new thiophosphoryl-based SCS pincer ligand leads to oxidative addition of an sp2–sp3 C–C bond as the only observed outcome, despite the presence of accessible sp3 C–H bonds. A DFT study reveals that the chemistry of the SCS system is controlled by π repulsion between occupied rhodium d orbitals and the lone-pair electrons on the two sulfur atoms. This repulsion gives rise to the thermodynamic selectivity for C–C over C–H cleavage, as it is attributed to the higher electronegativity of a methyl versus hydride ligand, thereby allowing more effective release of excessive π electron density. It is also demonstrated that the observed C–C and unobserved C–H cleavage pathways originate from a common intermediate that features a novel η3-C–C–H agostic interaction. The COE ligand is shown to play an important role by greatly stabilizing this intermediate, making it the only available entry point to both reaction pathways." @default.
- W2328066145 created "2016-06-24" @default.
- W2328066145 creator A5015331508 @default.
- W2328066145 creator A5026540940 @default.
- W2328066145 creator A5049737397 @default.
- W2328066145 creator A5050879584 @default.
- W2328066145 creator A5081692819 @default.
- W2328066145 creator A5086773368 @default.
- W2328066145 date "2011-12-28" @default.
- W2328066145 modified "2023-10-16" @default.
- W2328066145 title "Exclusive C–C Oxidative Addition in a Rhodium Thiophosphoryl Pincer Complex and Computational Evidence for an η<sup>3</sup>-C–C–H Agostic Intermediate" @default.
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