| Zdroj: |
Doyle, L R, Galpin, M R, Furfari, S K, Tegner, B E, Martínez-martínez, A J, Whitwood, A C, Hicks, S A, Lloyd-jones, G C, Macgregor, S A & Weller, A S 2022, ' Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex ', Organometallics . https://doi.org/10.1021/acs.organomet.1c00639 |
| Popis: |
The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2or D2was followed in situ by solid-state31P{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. |
