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.
Original language | English |
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Pages (from-to) | 284-292 |
Number of pages | 9 |
Journal | Organometallics |
Volume | 41 |
Issue number | 3 |
Early online date | 27 Jan 2022 |
DOIs | |
Publication status | Published - 14 Feb 2022 |
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Dive into the research topics of 'Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex'. Together they form a unique fingerprint.Datasets
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CCDC 2120252: Experimental Crystal Structure Determination
Doyle, L. R. (Creator), Galpin, M. R. (Creator), Furfari, S. K. (Creator), Tegner, B. E. (Creator), Martínez-Martínez, A. J. (Creator), Whitwood, A. C. (Creator), Hicks, S. A. (Creator), Lloyd-Jones, G. C. (Creator), Macgregor, S. A. (Creator) & Weller, A. S. (Creator), Cambridge Crystallographic Data Centre, 2022
DOI: 10.5517/ccdc.csd.cc295971
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