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Kozinets EM, Fekete M, Filippov OA, et al. Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study. Dalton Trans. 2013;42(32):11720-30doi: 10.1039/c3dt51429c.
Kozinets, E. M., Fekete, M., Filippov, O. A., Belkova, N. V., Shubina, E. S., Poli, R., Duckett, S. B., & Manoury, E. (2013). Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study. Dalton transactions (Cambridge, England : 2003), 42(32), 11720-30. https://doi.org/10.1039/c3dt51429c
Kozinets, Ekaterina M, et al. "Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study." Dalton transactions (Cambridge, England : 2003) vol. 42,32 (2013): 11720-30. doi: https://doi.org/10.1039/c3dt51429c
Kozinets EM, Fekete M, Filippov OA, Belkova NV, Shubina ES, Poli R, Duckett SB, Manoury E. Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study. Dalton Trans. 2013 Aug 28;42(32):11720-30. doi: 10.1039/c3dt51429c. Epub 2013 Jul 12. PMID: 23851567.
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Dalton Trans. 2013 Aug 28;42(32):11720-30. doi: 10.1039/c3dt51429c. Epub 2013 Jul 12.

Activation of a (cyclooctadiene) rhodium(I) complex supported by a chiral ferrocenyl phosphine thioether ligand for hydrogenation catalysis: a combined parahydrogen NMR and DFT study.

Dalton transactions (Cambridge, England : 2003)

Ekaterina M Kozinets, Marianna Fekete, Oleg A Filippov, Natalia V Belkova, Elena S Shubina, Rinaldo Poli, Simon B Duckett, Eric Manoury

Affiliations

  1. CNRS, LCC (Laboratoire de Chimie de Coordination), Toulouse, France.

PMID: 23851567 DOI: 10.1039/c3dt51429c

Abstract

The reaction of [RhCl(P,S(t)Bu)(COD)] (1) or [Rh(P,S(t)Bu)(COD)]BF4 (2) where (P,S(t)Bu) is CpFe[η(5)-1,2-C5H3(PPh2)(CH2S(t)Bu)] with H2 in MeOH gives rise to COD hydrogenation and formation of a solvent-stabilized product. The formation of hydride species cannot be observed in view of a very rapid H/D exchange between H2 and the solvent. Introduction of pyridine or acetonitrile slows down this exchange process and allows observation of diastereometric dihydride complexes, [Rh(P,S(t)Bu)(H)2(L)2](+), the stereochemistry of which was fully elucidated. The hydride site exchange rates have been derived from EXSY NMR experiments and used, with assistance from DFT calculation, to elucidate the isomerization and site exchange mechanisms.

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