Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane
- 作者: Nekrasov R.I.1, Peganova T.A.1, Kal´sin A.M.1, Belkova N.V.1
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隶属关系:
- Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
- 期: 卷 50, 编号 6 (2024)
- 页面: 394-401
- 栏目: Articles
- URL: https://journals.eco-vector.com/0132-344X/article/view/667594
- DOI: https://doi.org/10.31857/S0132344X24060053
- EDN: https://elibrary.ru/MVDOVM
- ID: 667594
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详细
The dehydrogenation of dimethylamine-borane (DMAB) catalyzed by the iminophosphonamide rhodium(III) complexes [Cp*RhCl{Ph2P(N–p-Tol)(NR)}] (Iа, R = p-Tol; Ib, R = Me) in situ formed fulvene [(η4-C5Me4CH2)Rh(NPN)] (IIa, IIb) and diene [(η4-C5Me5H)Rh(NPN)] (IIIa, IIIb) rhodium(I) derivatives is studied. Catalysts IIIa and IIIb turn out to be the most active and demonstrate a TOF activity of 110 (IIIа) and 540 h–1 (IIIb) at 40°С in toluene. The activity decreases significantly in more polar and coordinating THF. At the same time, the rate of DMAB dehydrogenation by complexes Iа and Ib is lower by 10–30 times, and fulvene complexes Iа and Ib are rapidly deactivated after the active initial period (<20% conversion). The kinetic studies show that the reaction has the first order with respect to the substrate and catalyst. The model 11В NMR experiments confirm that the reaction proceeds via the intermediate formation of a monomer Me2N=BH2, which rapidly dimerizes to (Me2N–BH2)2. The mechanism of DMAB dehydrogenation with the formation of unstable hydride intermediate [Cp*RhH{Ph2P(N–p-Tol)(NR)}] (IVa, IVb) is proposed on the basis of the preliminarily 31Р NMR results and published data.
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作者简介
R. Nekrasov
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Email: nataliabelk@ineos.ac.ru
俄罗斯联邦, Moscow
T. Peganova
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Email: nataliabelk@ineos.ac.ru
俄罗斯联邦, Moscow
A. Kal´sin
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
Email: nataliabelk@ineos.ac.ru
俄罗斯联邦, Moscow
N. Belkova
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
编辑信件的主要联系方式.
Email: nataliabelk@ineos.ac.ru
俄罗斯联邦, Moscow
参考
- Colebatch A.L., Weller A.S. // Chem. Eur. J. 2019. V. 25. P. 1379. https://doi.org/10.1002/chem.201804592
- Staubitz A., Robertson A.P.M., Manners I. // Chem. Rev. 2010. V. 110. p. 4079. https://doi.org/10.1021/cr100088b
- Du V.A., Jurca T., Whittell G.R., Manners I. // Dalton Trans. 2016. V. 45. P. 1055. https://doi.org/10.1039/C5DT03324A
- Resendiz-Lara D.A., Stubbs N.E., Arz M.I. et al. // Chem. Commun. 2017. V. 53. P. 11701.
- Kumar A., Daw P., Milstein D. et al. // Chem. Rev. 2022. V. 122. P. 385. https://doi.org/10.1021/acs.chemrev.1c00412
- Alig L., Fritz M., Schneider S. et al. // Chem. Rev. 2019. V. 119. P. 2681. https://doi.org/10.1021/acs.chemrev.8b00555
- Glüer A., Förster M., Celinski V. R. et al. // ACS Catal. 2015. V. 5. P. 7214. https://doi.org/10.1021/acscatal.5b02406
- Luconi L., Osipova E. S., Giambastiani G. et al. // Organometallics. 2018. V. 37. P. 3142. https://doi.org/10.1021/acs.organomet.8b00488
- Todisco., S., Luconi., L., Giambastiani., G et al. // Inorg. Chem. 2017. V. 56. P. 4296. https://doi.org/10.1021/acs.inorgchem.6b02673
- Titova. E.M., Osipova. E.S., Pavlov. A.A. et al. // ACS Catal. 2017. V. 7. P. 2325. https://doi.org/10.1021/acscatal.6b03207
- Sewell L.J., Huertos M.A., Dickinson M.E. et al. // Inorg. Chem. 2013. V. 52. P. 4509. https://doi.org/10.1021/ic302804d
- Johnson H.C., Leitao E.M., Whittell G.R. et al. // J. Am. Chem. Soc. 2014. V. 136. P. 9078. https://doi.org/10.1021/ja503335g
- Douglas T.M., Chaplin A.B., Weller A S. et al. // J. Am. Chem. Soc. 2009. V. 131. P. 15440. http://dx.doi.org/10.1021/ja906070r
- Kirkina V.A., Osipova E.S., Filippov O.A. et al. // Mendeleev Commun. 2020. V. 30. P. 276. https://doi.org/10.1016/j.mencom.2020.05.004
- Brodie C.N., Sotorrios L., Boyd T.M. et al. // ACS Catal. 2022, vol. 12. P. 13050. https://doi.org/10.1021/acscatal.2c03778
- Brodie C.N., Boyd T.M., Sotorríos L. et al. // J. Am. Chem. Soc. 2021. V. 143. P. 21010. https://doi.org/10.1021/jacs.1c10888
- White C., Yates A., Maitlis P.M. et al. // Inorg. Synth. 1992. V. 29. P. 228. https://doi.org/10.1002/9780470132609.ch53
- Nekrasov R.I., Peganova T.A., Fedyanin I.V. et al. // Inorg. Chem. 2022. V. 61. P. 16081. https://doi.org/10.1021/acs.inorgchem.2c02478
- Kruger C.R., Niederprum H. // Inorg. Synth. 1966. V. 8. P. 15.
- Pal S., Kusumoto S., Nozaki K. // Organometallics. 2018. V. 37. P. 906. https://doi.org/10.1021/acs.organomet.7b00889
- Sinopalnikova I.S., Peganova T.A., Belkova N.V. et al. // Eur. J. Inorg. Chem. 2018. V. 2018. P. 2285. https://doi.org/10.1002/ejic.20170134423
- Pal S., Iwasaki T., Nozaki K. // Dalton Trans. 2021, V. 50. P. 7938. https://doi.org/10.1039/D1DT01705E
- Dallanegra R., Robertson A.P.M., Chaplin A. B. et al. // Chem. Commun. 2011. V. 47. P. 3763. https://doi.org/10.1039/C0CC05460G
- Gulyaeva E.S., Osipova E.S., Kovalenko S.A. et al. // Chem. Sci. 2024. V. 15. P. 1409. https://doi.org/10.1039/D3SC05356C
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