New nickel pincer complexes based on pentamethylruthenocene

Capa

Citar

Texto integral

Acesso aberto Acesso aberto
Acesso é fechado Acesso está concedido
Acesso é fechado Somente assinantes

Resumo

New nickel(II) pincer complexes based on the pentamethylruthenocene, NiCl[{2,5-(R2PCH2)2C5H2}Ru(Cp*)] (Cp* = C5Me5, Ia: R = tBu; Ib: R = iPr) were synthesized via a two-step route starting from the 1,3-functionally substituted diol {1,3-(HOCH2)C5H3}Ru(Cp*). In the first step, diol was reacted with dialkylphosphines (tBu2PH, iPr2PH) in acetic acid to give diphosphines {1,3-(R2PCH2)2C5H3}Ru(Cp*) (R = tBu; iPr), which were not isolated in a pure state, but after the removal AcOH, was immediately subjected to cyclometallation with nickel(II) chloride hexahydrate in the presence of pyridine. After all purification procedures, the yields of products Ia and Ib were 31 and 16%, respectively. The complexes were fully characterized by 1H, 31P{1H}, and 13C{1H} NMR spectroscopy. The purity of the products was confirmed by elemental analysis. The structure of complex Ia was established by single-crystal X-ray diffraction (CCDC № 2408463).

Texto integral

Acesso é fechado

Sobre autores

S. Safronov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Autor responsável pela correspondência
Email: sergiosfr.svs@gmail.com
Rússia, Moscow

Yu. Nelyubina

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: sergiosfr.svs@gmail.com
Rússia, Chernogolovka

Bibliografia

  1. Eberhardt N.A., Guan H. // Chem. Rev. 2016. V. 116. P. 8373. https://doi.org/10.1021/acs.chemrev.6b00259
  2. Гафуров З.Н., Кагилев А.А., Кантюков А.О. и др. // Изв. АН. Сер. хим. 2018. № 3. С. 385. (Gafurov Z.N., Kagilev A.A., Kantyukov A.O. et al. // Russ. Chem. Bull. 2018. V. 67. P. 385). https://doi.org/10.1007/s11172-018-2086-7
  3. Arora V., Narjinari H., Nandi P.G., Kumar A. // Dalton Trans. 2021. V. 50. P. 3394. https://doi.org/10.1039/d0dt03593a
  4. Chacraborty S., Bhattacharya P., Dai H., Guan H. // Acc. Chem. Res. 2015. V. 48. P. 1995. https://doi.org/10.1021/acs.accounts.5b00055
  5. Adhikary A., Guan H. // ACS Catal. 2015. V. 5. P. 6858. https://doi.org/10.1021/acscatal.5b01688
  6. Сафронов С.В., Куклин С.А., Абрамова Н.В., Нелюбина Ю.В. // Изв. АН. Сер. хим. 2024. № 10. С. 2831 (Safronov S.V., Kuklin S.A., Abramova N.V., Nelyubina Yu.V. // Russ. Chem. Bull. 2024. V. 73. P. 2831). https://doi.org/10.1007/s11172-024-4399-z
  7. Куклин С.А., Долгушин Ф.М., Петровский П.В., Коридзе А.А. // Изв. АН. Сер. хим. 2006. № 11. С. 1879 (Kuklin S.A., Dolgushin F.M., Petrovskii P.V., Koridze A.A. // Russ. Chem. Bull. 2006. V. 55. P. 1950). https://doi.org/10.1007/s11172-006-0536-0
  8. Сафронов С.В., Шелоумов А.М., Крейндлин А.З. и др. // Изв. АН. Сер. хим. 2010. № 9. С. 1694 (Safronov S.V., Sheloumov A.M., Kreindlin A.Z. et al. // Russ. Chem. Bull. (Int. Ed.). 2010. V. 59. P. 1740). https://doi.org/10.1007/s11172-010-0306-x
  9. Safronov S.V., Osipova E.S., Nelyubina Yu.V. et al. // Molecules. 2020. V. 25. P. 2236. https://doi.org/10.3390/molecules25092236
  10. Zhu K., Achord P.D., Zhang X. et al. // J. Am. Chem. Soc. 2004. V. 126. P. 13044. https://doi.org/10.1021/ja047356l
  11. Sheldrick G.M. // Acta Crystallogr. A. 2008. V. 64. P. 112. https://doi.org/10.1107/S0108767307043930
  12. Dolomanov O.V., Bourhis L.J., Gildea R.J. et al. // J. Appl. Crystallogr. 2009. V. 42. P. 339. https://doi.org/10.1107/S0021889808042726
  13. Koridze A.A., Kuklin S.A., Sheloumov A.M et al. // Organometallics. 2004. V. 23. P. 4585. https://doi.org/10.1021/om0497285
  14. Bickert P., Hildebrandt B., Hafner K. // Organometallics. 1984. V. 3. P. 653. https://doi.org/10.1021/om00083a001
  15. Сафронов С.В. // Изв. АН. Сер. хим. 2022. № 2. С. 363 (Safronov S.V. // Russ. Chem. Bull. 2022. V. 71. P. 363). https://doi.org/10.1007/s11172-022-3420-7
  16. Сафронов C.В., Коридзе А.А. // Изв. АН. Сер. хим. 2018. № 7. С. 1247 (Safronov S.V., Koridze A.A. // Russ. Chem. Bull. 2018. V. 67. P. 1247). https://doi.org/10.1007/s11172-018-2208-2
  17. Pandarus V., Zargarian D. // Organometallics. 2007. V. 26. P. 4321. https://doi.org/ 10.1021/om700400x
  18. Gafurov Z.N., Kantyukov A.O., Kagilev A.A. et al. // Molecules. 2021. V. 26. P. 4063. https://doi.org/10.3390/molecules26134063

Arquivos suplementares

Arquivos suplementares
Ação
1. JATS XML
Baixar
2. Fig. 1. General view of complex Ia with atoms represented by thermal vibration ellipsoids (p = 50%). The molecular structure of one of the two crystallographically independent molecules of Ia is shown. Hydrogen atoms are not shown, and numbering is given only for metal ions, heteroatoms, and selected carbon atoms.

Baixar (196KB)
Metadados
3. Scheme 1. Preparation of diphosphines {1,3-(R2PCH2)2C5H3}Ru(Cp*) (R = tBu, iPr) and pincer nickel complexes Ia, Ib.

Baixar (142KB)
Metadados

Declaração de direitos autorais © Российская академия наук, 2025