Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex

Laurence R. Doyle*, Martin R. Galpin, Samantha K. Furfari, Bengt E. Tegner, Antonio J. Martínez-Martínez, Adrian C. Whitwood, Scott A. Hicks, Guy C. Lloyd-Jones, Stuart A. MacGregor, Andrew S. Weller

*Corresponding author for this work

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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 η22-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 languageEnglish
Pages (from-to)284–292
Number of pages9
JournalOrganometallics
Volume41
Issue number3
Early online date27 Jan 2022
DOIs
Publication statusPublished - 14 Feb 2022

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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