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

ABSTRACT: The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy₂P(CH₂)₃PCy₂)(COD)][BAr^F ₄] (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)][BAr^F ₄]. Using D₂, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an

SUBMITTER: Doyle LR 

PROVIDER: S-EPMC8900153 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature