Hydride transfer from rhodium complexes to triethylborane

Daniel L DuBois, Daniel M. Blake, Alex Miedaner, Calvin J. Curtis, M. R. DuBois, James A. Franz, John Linehan

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

The hydrides HRh(depe) 2 and HRh(dmpe) 2 (depe = Et 2PCH 2CH 2PEt 2, dmpe = Me 2PCH 2CH 2PMe 2) have thermodynamic hydride donor abilities comparable to LiHBEt 3, as indicated by their ability to transfer a hydride ligand to Et 3B to sequentially form [Et 3BHBEt 3] - and [HBEt 3] -. HRh(depe) 2 and HRh(dmpe) 2 can be generated from [Rh(dmpe) 2](CF 3SO 3) and [Rh(depe) 2](CF 3SO 3) and hydrogen gas in the presence of a strong base such as potassium tert-butoxide or lithium diisopropylamide. This reaction proceeds through the oxidative addition of hydrogen to form the [H 2Rh(diphosphine) 2](CF 3SO 3) complexes, followed by deprotonation. The oxidative addition of H 2 is favored by diphosphine ligands with electron-donating substituents and large chelate bites. In the present study, the driving force for oxidative addition of H 2 follows the order [Rh(dmpe) 2](CF 3SO 3) > [Rh(depe) 2](CF 3SO 3) > [Rh(dppe) 2](CF 3SO 3) with [Rh(dmpe) 2]-(CF 3SO 3) binding H 2 more strongly than [Rh(dppe) 2](CF 3SO 3) (dppe = Ph 2PCH 2CH 2PPh 2) by at least 2.7 kcal/mol. The effect of the chelate bite size is larger. [H 2Rh(depx) 2](CF 3SO 3) (depx = 1,2-(Et 2-PCH 2) 2C 6H 4) binds H 2 more strongly than [Rh(depe) 2](CF 3SO 3) by 12 kcal/mol. An understanding of both hydrogen activation and hydride donor abilities is important for developing powerful hydride donors from H 2.

Original languageEnglish
Pages (from-to)4414-4419
Number of pages6
JournalOrganometallics
Volume25
Issue number18
DOIs
Publication statusPublished - Aug 28 2006

Fingerprint

Rhodium
rhodium
Hydrides
hydrides
Hydrogen
chelates
hydrogen
Ligands
Deprotonation
ligands
potassium
lithium
Gases
Chemical activation
triethylborane
Thermodynamics
activation
thermodynamics
Electrons
gases

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

DuBois, D. L., Blake, D. M., Miedaner, A., Curtis, C. J., DuBois, M. R., Franz, J. A., & Linehan, J. (2006). Hydride transfer from rhodium complexes to triethylborane. Organometallics, 25(18), 4414-4419. https://doi.org/10.1021/om060584z

Hydride transfer from rhodium complexes to triethylborane. / DuBois, Daniel L; Blake, Daniel M.; Miedaner, Alex; Curtis, Calvin J.; DuBois, M. R.; Franz, James A.; Linehan, John.

In: Organometallics, Vol. 25, No. 18, 28.08.2006, p. 4414-4419.

Research output: Contribution to journalArticle

DuBois, DL, Blake, DM, Miedaner, A, Curtis, CJ, DuBois, MR, Franz, JA & Linehan, J 2006, 'Hydride transfer from rhodium complexes to triethylborane', Organometallics, vol. 25, no. 18, pp. 4414-4419. https://doi.org/10.1021/om060584z
DuBois DL, Blake DM, Miedaner A, Curtis CJ, DuBois MR, Franz JA et al. Hydride transfer from rhodium complexes to triethylborane. Organometallics. 2006 Aug 28;25(18):4414-4419. https://doi.org/10.1021/om060584z
DuBois, Daniel L ; Blake, Daniel M. ; Miedaner, Alex ; Curtis, Calvin J. ; DuBois, M. R. ; Franz, James A. ; Linehan, John. / Hydride transfer from rhodium complexes to triethylborane. In: Organometallics. 2006 ; Vol. 25, No. 18. pp. 4414-4419.
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abstract = "The hydrides HRh(depe) 2 and HRh(dmpe) 2 (depe = Et 2PCH 2CH 2PEt 2, dmpe = Me 2PCH 2CH 2PMe 2) have thermodynamic hydride donor abilities comparable to LiHBEt 3, as indicated by their ability to transfer a hydride ligand to Et 3B to sequentially form [Et 3BHBEt 3] - and [HBEt 3] -. HRh(depe) 2 and HRh(dmpe) 2 can be generated from [Rh(dmpe) 2](CF 3SO 3) and [Rh(depe) 2](CF 3SO 3) and hydrogen gas in the presence of a strong base such as potassium tert-butoxide or lithium diisopropylamide. This reaction proceeds through the oxidative addition of hydrogen to form the [H 2Rh(diphosphine) 2](CF 3SO 3) complexes, followed by deprotonation. The oxidative addition of H 2 is favored by diphosphine ligands with electron-donating substituents and large chelate bites. In the present study, the driving force for oxidative addition of H 2 follows the order [Rh(dmpe) 2](CF 3SO 3) > [Rh(depe) 2](CF 3SO 3) > [Rh(dppe) 2](CF 3SO 3) with [Rh(dmpe) 2]-(CF 3SO 3) binding H 2 more strongly than [Rh(dppe) 2](CF 3SO 3) (dppe = Ph 2PCH 2CH 2PPh 2) by at least 2.7 kcal/mol. The effect of the chelate bite size is larger. [H 2Rh(depx) 2](CF 3SO 3) (depx = 1,2-(Et 2-PCH 2) 2C 6H 4) binds H 2 more strongly than [Rh(depe) 2](CF 3SO 3) by 12 kcal/mol. An understanding of both hydrogen activation and hydride donor abilities is important for developing powerful hydride donors from H 2.",
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