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- W4210596199 abstract "The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson-Mehl-Avrami-Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment." @default.
- W4210596199 created "2022-02-08" @default.
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- W4210596199 date "2022-01-27" @default.
- W4210596199 modified "2023-10-14" @default.
- W4210596199 title "Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex" @default.
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- W4210596199 doi "https://doi.org/10.1021/acs.organomet.1c00639" @default.
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