Hyperpolarization effects in parahydrogen activation with pnictogen biradicaloids : metal‐free PHIP and SABRE
Zhivonitko, Vladimir V.; Beer, Henrik; Zakharov, Danila O.; Bresien, Jonas; Schulz, Axel (2021-03-16)
V. V. Zhivonitko, H. Beer, D. O. Zakharov, J. Bresien, A. Schulz, ChemPhysChem 2021, 22, 813. https://doi.org/10.1002/cphc.202100141
© 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
https://creativecommons.org/licenses/by/4.0/
https://urn.fi/URN:NBN:fi-fe2021051229792
Tiivistelmä
Abstract
Biradicaloids attract attention as a novel class of reagents that can activate small molecules such as H₂, ethylene and CO₂. Herein, we study activation of parahydrogen (nuclear spin‐0 isomer of H₂) by a number of 4‐ and 5‐membered pnictogen biradicaloids based on hetero‐cyclobutanediyl [X(μ‐NTer)₂Z] and hetero‐cyclopentanediyl [X(μ‐NTer)₂ZC(NDmp)] moieties (X,Z=P,As; Ter=2,6‐Mes₂−C₆H₃, Dmp=2,6‐Me₂−C₆H₃). The concerted mechanism of this reaction allowed observing strong nuclear spin hyperpolarization effects in ¹H and ³¹P NMR experiments. Signal enhancements from two to four orders of magnitude were detected at 9.4 T depending on the structure. It is demonstrated that 4‐membered biradicaloids activate H₂ reversibly, leading to SABRE (signal amplification by reversible exchange) hyperpolarization of biradicaloids themselves and their H₂ adducts. In contrast, the 5‐membered counterparts demonstrate rather irreversible parahydrogen activation resulting in hyperpolarized H₂ adducts only. Kinetic measurements provided parameters to support experimental observations.
Kokoelmat
- Avoin saatavuus [31993]