NONEQUILIBRIUM NUCLEAR SPIN STATES OF ETHYLENE DURING ACETYLENE HYDROGENATION WITH PARAHYDROGEN OVER IMMOBILIZED IRIDIUM COMPLEXES

I. V. Skovpin; Сковпин И. В.; S. V. Sviyazov; Свиязов С. В.; D. B. Burueva; Буруева Д. Б.; L. M. Kovtunova; Ковтунова Л. М.; A. V. Nartova; Нартова А. В.; R. I. Kvon; Квон Р. И.; V. I. Bukhtiyarov; Бухтияров В. И.; I. V. Koptyug; Коптюг И. В.

doi:10.31857/S2686953522600933

NONEQUILIBRIUM NUCLEAR SPIN STATES OF ETHYLENE DURING ACETYLENE HYDROGENATION WITH PARAHYDROGEN OVER IMMOBILIZED IRIDIUM COMPLEXES

Authors: Skovpin I.V.¹, Sviyazov S.V.¹^,2, Burueva D.B.¹, Kovtunova L.M.¹^,3, Nartova A.V.³, Kvon R.I.³, Bukhtiyarov V.I.³, Koptyug I.V.¹
Affiliations:
1. International Tomography Center, Siberian Branch of the Russian Academy of Sciences
2. Novosibirsk State University
3. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences
Issue: Vol 512, No 1 (2023)
Pages: 120-129
Section: ФИЗИЧЕСКАЯ ХИМИЯ
URL: https://journals.rcsi.science/2686-9535/article/view/247191
DOI: https://doi.org/10.31857/S2686953522600933
EDN: https://elibrary.ru/HPUROO
ID: 247191

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Abstract

In this work rhodium and iridium immobilized complexes were prepared and characterized by X-ray photoelectron spectroscopy. For the first time, hyperpolarized ¹³C-ethylene was detected directly in the gas phase during acetylene hydrogenation with parahydrogen on immobilized iridium complexes. The line shape of polarized ¹³С‑ethylene unambiguously indicates that the hydrogen addition to the triple bond of acetylene on immobilized iridium complexes proceeds via syn-addition. It has been shown that the selective acetylene hydrogenation with parahydrogen over immobilized iridium complexes is an effective chemical method for enriching the nuclear spin isomers of ethylene.

Keywords

hyperpolarization, parahydrogen, parahydrogen-induced polarization, NMR, heterogeneous catalysis, immobilized complexes, XPS, selective hydrogenation, ethylene

References

Bos A.N.R., Westerterp K.R. // Chem. Eng. Process. Process Intensif. 1993. V. 32. P. 1–7. https://doi.org/10.1016/0255-2701(93)87001-B
Zhivonitko V.V., Kovtunov K.V., Chapovsky P.L., Kop-tyug I.V. // Angew. Chem. Int. Ed. 2013. V. 52. P. 13251–13255. https://doi.org/10.1002/anie.201307389
Chapovsky P.L., Zhivonitko V.V., Koptyug I.V. // J. Phys. Chem. A. 2013. V. 117. P. 9673–9683. https://doi.org/10.1021/jp312322f
Гельмуханов Ф.Х., Шалагин А.М. // Письма в ЖЭТФ. 1979. V. 29. P. 773–776.
Sun Z.-D., Takagi K., Matsushima F. // Science. 2005. V. 310. P. 1938–1941. https://doi.org/10.1126/science.1120037
Eills J., Budker D., Cavagnero S., Chekmenev E.Y., Elliott S.J., Jannin S., Lesage A., Matysik J., Meersmann T., Prisner T., Reimer J.A., Yang H., Koptyug I.V. // Chem. Rev. 2023. V. 123. P. 1417–1551. https://doi.org/10.1021/acs.chemrev.2c00534
Ковтунов К.В., Буруева Д.Б., Свиязов С.В., Сальников О.Г., Гудсон Б.М., Чекменев Э.Ю., Коптюг И.В. // Изв. АН. Сер. Хим. 2021. V. 12. P. 2382–2389.
Покочуева Е.В., Святова А.И., Буруева Д.Б., Коптюг И.В. // Изв. АН. Сер. Хим. 2023. V. 1. P. 1–19.
Duckett S.B., Mewis R.E. // Acc. Chem. Res. 2012. V. 45 P. 1247–1257. https://doi.org/10.1021/ar2003094
Koptyug I.V., Kovtunov K.V., Burt S.R., Anwar M.S., Hilty C., Han S.-I., Pines A., Sagdeev R.Z. // J. Am. Chem. Soc. 2007. V. 129. P. 5580–5586. https://doi.org/10.1021/ja068653o
Kovtunov K.V., Beck I.E., Bukhtiyarov V.I., Koptyug I.V. // Angew. Chem. Int. Ed. 2008. V. 47. P. 1492–1495. https://doi.org/10.1002/anie.200704881
Kovtunov K.V., Zhivonitko V.V., Skovpin I.V., Barskiy D.A., Koptyug I.V. // Top. Curr. Chem. 2013. V. 338. P. 123–180. https://doi.org/10.1007/128_2012_371
Pokochueva E.V., Burueva D.B., Kovtunova L.M., Bukhtiyarov A.V., Gladky A.Yu., Kovtunov K.V., Koptyug I.V., Bukhtiyarov V.I. // Faraday Discuss. 2021. V. 229. P. 161–175. https://doi.org/10.1039/C9FD00138G
Burueva D.B., Kovtunov K.V., Bukhtiyarov A.V., Barskiy D.A., Prosvirin I.P., Mashkovsky I.S., Baeva G.N., Bukhtiyarov V.I., Stakheev A.Yu., Koptyug I.V. // Chem. Eur. J. 2018. V. 24. P. 2547–2553. https://doi.org/10.1002/chem.201705644
Zhao E.W., Maligal-Ganesh R., Xiao C., Goh T.-W., Qi Z., Pei Y., Hagelin-Weaver H.E., Huang W., Bowers C.R. // Angew. Chem. Int. Ed. 2017. V. 56. P. 3925–3929. https://doi.org/10.1002/anie.201701314
Corma A., Salnikov O.G., Barskiy D.A., Kovtunov K.V., Koptyug I.V. // Chem. Eur. J. 2015. V. 21. P. 7012–7015. https://doi.org/10.1002/chem.201406664
Skovpin I.V., Zhivonitko V.V., Koptyug I.V. // Appl. Magn. Reson. 2011. V. 41. P. 393–410. https://doi.org/10.1007/s00723-011-0255-z
Skovpin I.V., Zhivonitko V.V., Kaptein R., Koptyug I.V. // Appl. Magn. Reson. 2013. V. 44. P. 289–300. https://doi.org/10.1007/s00723-012-0419-5
Skovpin I.V., Zhivonitko V.V., Prosvirin I.P., Khabibulin D.F., Koptyug I.V. // Z. Phys. Chem. 2017. V. 231. P. 575–592. https://doi.org/10.1515/zpch-2016-0824
Skovpin I.V., Kovtunova L.M., Nartova A.V., Kvon R.I., Bukhtiyarov V.I., Koptyug I.V. // Catal. Sci. Technol. 2022. V. 12. P. 3247–3253. https://doi.org/10.1039/D1CY02258J
Crabtree R.H., Morris G.E. // J. Organomet. Chem. 1977. V. 135. P. 395–403. https://doi.org/10.1016/S0022-328X(00)88091-2
Yamada T., Matsuo T., Ogawa A., Ichikawa T., Kobayashi Y., Masuda H., Miyamoto R., Bai H., Meguro K., Sawama Y., Monguchi Y., Sajiki H. // Org. Process Res. Dev. 2018. V. 23. P. 462–469. https://doi.org/10.1021/acs.oprd.8b00291
Huang L., Ang T.P., Wang Z., Tan J., Chen J., Wong P.K. // Inorg. Chem. 2011. V. 50. P. 2094–2111. https://doi.org/10.1021/ic100824e
Crudden C.M., Sateesh M., Lewis R. // J. Am. Chem. Soc. 2005. V. 127. P. 10045–10050. https://doi.org/10.1021/ja0430954
Holsboer F., Beck W., Bartunik H.D. // J. Chem. Soc., Dalt. Trans. 1973. P. 1828–1829. https://doi.org/10.1039/DT9730001828
Fernando N.K., Cairns A.B., Murray C.A., Thompson A.L., Dickerson J.L., Garman E.F., Ahmed N., Ratcliff L.E., Regoutz A. // J. Phys. Chem. A. 2021. V. 125. P. 7473–7488. https://doi.org/10.1021/acs.jpca.1c05759
Bowers C.R., Weitekamp D.P. // J. Am. Chem. Soc. 1987. V. 109. P. 5541–5542. https://doi.org/10.1021/ja00252a049
Salnikov O.G., Kovtunov K.V., Barskiy D.A., Khudorozhkov A.K., Inozemtseva E.A., Prosvirin I.P., Bukhtiya-rov V.I., Koptyug I.V. // ACS Catal. 2014. V. 4. P. 2022–2028. https://doi.org/10.1021/cs500426a
Giordano G., Crabtree R.H., Heintz R.M., Forster D., Morris D.E. Di-μ-chloro-bis(η4-1,5-cyclooctadlene) dirhodium (I). In: Inorganic syntheses. V. 19. Shri-ver D.F. (Ed.). John Wiley & Sons, 1979. P. 218–220. https://doi.org/10.1002/9780470132500.ch50
Moulder J.F., Stickle W.F., Sobol P.E., Bomben K.D. Handbook of X-ray photoelectron spectroscopy. 2nd edn. Perkin-Elmer Corp., Eden Priarie, MN, USA, 1992.
XPSPEAK, свободно распространяемое программное обеспечение для анализа спектров РФЭС // http://xpspeak.software.informer.com/4.1/ (ссылка активна на 27.12.2022).
Квон Р.И., Нартова АВ., Ковтунова Л.М., Бухтияров В.И. // Журн. структ. хим. 2023. V. 64. P. 106142. https://doi.org/10.26902/JSC_id106142