Vladimir V. Zhivonitko, Ivan V. Skovpin, Kai C. Szeto, Mostafa Taoufik, and Igor V. Koptyug, Parahydrogen-Induced Polarization Study of the Silica-Supported Vanadium Oxo Organometallic Catalyst The Journal of Physical Chemistry C 2018 122 (9), 4891-4900, DOI: 10.1021/acs.jpcc.7b12069
Parahydrogen-induced polarization study of the silica-supported vanadium oxo organometallic catalyst
|Author:||Zhivonitko, Vladimir V.1,2,3; Skovpin, Ivan V.2,3; Szeto, Kai C.4;|
1NMR Research Unit, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
2Laboratory of Magnetic Resonance Microimaging, International Tomography Center SB RAS, Institutskaya Street 3A, 630090 Novosibirsk, Russia
3Department of Natural Sciences, Novosibirsk State University, Pirogova Street 2, 630090 Novosibirsk, Russia
4Laboratoire de Chimie, Catalyse, Polymères et Procédés, UMR 5265 CNRS/ESCPE-Lyon/UCBL, ESCPE Lyon, F-308-43, Boulevard du 11 Novembre 1918, F-69616 Villeurbanne Cedex, France
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2018051724183
American Chemical Society,
|Publish Date:|| 2019-02-15
Parahydrogen can be used in catalytic hydrogenations to achieve substantial enhancement of NMR signals of the reaction products and in some cases of the reaction reagents as well. The corresponding nuclear spin hyperpolarization technique, known as parahydrogen-induced polarization (PHIP), has been applied to boost the sensitivity of NMR spectroscopy and magnetic resonance imaging by several orders of magnitude. The catalyst properties are of paramount importance for PHIP because the addition of parahydrogen to a substrate must be pairwise. This requirement significantly narrows down the range of the applicable catalysts. Herein, we study an efficient silica-supported vanadium oxo organometallic complex (VCAT) in hydrogenation and dehydrogenation reactions in terms of efficient PHIP production. This is the first example of group 5 catalyst used to produce PHIP. Hydrogenations of propene and propyne with parahydrogen over VCAT demonstrated production of hyperpolarized propane and propene, respectively. The achieved NMR signal enhancements were 200−300-fold in the case of propane and 1300-fold in the case of propene. Propane dehydrogenation in the presence of parahydrogen produced no hyperpolarized propane, but instead the hyperpolarized side-product 1-butene was detected. Test experiments of other group 5 (Ta) and group 4 (Zr) catalysts showed a much lower efficiency in PHIP as compared to that of VCAT. The results prove the general conclusion that vanadium-based catalysts and other group 4 and group 5 catalysts can be used to produce PHIP. The hydrogenation/dehydrogenation processes, however, are accompanied by side reactions leading, for example, to C4, C2, and C1 side products. Some of the side products like 1-butene and 2-butene were shown to appear hyperpolarized, demonstrating that the reaction mechanism includes pairwise parahydrogen addition in these cases as well.
The journal of physical chemistry. C
|Pages:||4891 - 4900|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
114 Physical sciences
116 Chemical sciences
I.V.S. thanks RFBR (16-33-60198) and I.V.K. and V.V.Z. thank RFBR (17-54-33037) for financial support of the research. The authors thank FASO Russia (0333-2017-0002) for basic funding. V.V.Z. thanks University of Oulu (Kvantum Institute) for financial support.
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The journal of physical chemistry. C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, https://doi.org/10.1021/acs.jpcc.7b12069.