Pendant bases as proton relays in iron hydride and dihydrogen complexes

Renee M. Henry, Richard K. Shoemaker, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

90 Citations (Scopus)

Abstract

The complex trans-[HFe(PNP)(dmpm)(CH3CN)]BPh4, 3, (where PNP is Et2PCH2N(CH3)CH 2PEt2 and dmpm is Me2PCH2PMe 2) can be successively protonated in two steps using increasingly strong acids. Protonation with 1 equiv of p-cyanoanilinium tetrafluoroborate in acetone-d6 at -80 °C results in ligand protonation and the formation of endo (4a) and exo (4b) isomers of frans-[HFe(PNHP)(dmpm)(CH 3CN)]-(BPFu)2. The endo isomer undergoes rapid intramolecular proton/hydride exchange with an activation barrier of 12 kcal/mol. The exo isomer does not exchange. Studies of the reaction of 3 with a weaker acid (anisidinium tetrafluoroborate) in acetonitrile indicate that a rapid intermolecular proton exchange interconverts isomers 4a and 4b, and a pKa value of 12 was determined for these two isomers. Protonation of 3 with 2 equiv of triflic acid results in the protonation of both the PNP ligand and the metal hydride to form the dihydrogen complex [(H2)Fe(PNHP) (dmpm)(CH3CN)]3+, 11. Studies of related complexes [HFe(PNP)(dmpm)(CO)]+ (12) and [HFe(depp)(dmpm)(CH 3CN)]+ (10) (where depp is bis(diethylphosphino)propane) confirm the important roles of the pendant base and the ligand trans to the hydride ligand in the rapid intra- and intermolecular hydride/proton exchange reactions observed for 4. Features required for an effective proton relay and their potential relevance to the iron-only hydrogenase enzymes are discussed.

Original languageEnglish
Pages (from-to)3002-3010
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number9
DOIs
Publication statusPublished - Mar 8 2006

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Hydrides
Isomers
Protonation
Protons
Iron
Ligands
Ion exchange
Acids
Propane
Carbon Monoxide
Hydrogenase
Acetone
Acetonitrile
Metals
Enzymes
Chemical activation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Pendant bases as proton relays in iron hydride and dihydrogen complexes. / Henry, Renee M.; Shoemaker, Richard K.; DuBois, Daniel L; DuBois, M. Rakowski.

In: Journal of the American Chemical Society, Vol. 128, No. 9, 08.03.2006, p. 3002-3010.

Research output: Contribution to journalArticle

Henry, Renee M. ; Shoemaker, Richard K. ; DuBois, Daniel L ; DuBois, M. Rakowski. / Pendant bases as proton relays in iron hydride and dihydrogen complexes. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 9. pp. 3002-3010.
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abstract = "The complex trans-[HFe(PNP)(dmpm)(CH3CN)]BPh4, 3, (where PNP is Et2PCH2N(CH3)CH 2PEt2 and dmpm is Me2PCH2PMe 2) can be successively protonated in two steps using increasingly strong acids. Protonation with 1 equiv of p-cyanoanilinium tetrafluoroborate in acetone-d6 at -80 °C results in ligand protonation and the formation of endo (4a) and exo (4b) isomers of frans-[HFe(PNHP)(dmpm)(CH 3CN)]-(BPFu)2. The endo isomer undergoes rapid intramolecular proton/hydride exchange with an activation barrier of 12 kcal/mol. The exo isomer does not exchange. Studies of the reaction of 3 with a weaker acid (anisidinium tetrafluoroborate) in acetonitrile indicate that a rapid intermolecular proton exchange interconverts isomers 4a and 4b, and a pKa value of 12 was determined for these two isomers. Protonation of 3 with 2 equiv of triflic acid results in the protonation of both the PNP ligand and the metal hydride to form the dihydrogen complex [(H2)Fe(PNHP) (dmpm)(CH3CN)]3+, 11. Studies of related complexes [HFe(PNP)(dmpm)(CO)]+ (12) and [HFe(depp)(dmpm)(CH 3CN)]+ (10) (where depp is bis(diethylphosphino)propane) confirm the important roles of the pendant base and the ligand trans to the hydride ligand in the rapid intra- and intermolecular hydride/proton exchange reactions observed for 4. Features required for an effective proton relay and their potential relevance to the iron-only hydrogenase enzymes are discussed.",
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AB - The complex trans-[HFe(PNP)(dmpm)(CH3CN)]BPh4, 3, (where PNP is Et2PCH2N(CH3)CH 2PEt2 and dmpm is Me2PCH2PMe 2) can be successively protonated in two steps using increasingly strong acids. Protonation with 1 equiv of p-cyanoanilinium tetrafluoroborate in acetone-d6 at -80 °C results in ligand protonation and the formation of endo (4a) and exo (4b) isomers of frans-[HFe(PNHP)(dmpm)(CH 3CN)]-(BPFu)2. The endo isomer undergoes rapid intramolecular proton/hydride exchange with an activation barrier of 12 kcal/mol. The exo isomer does not exchange. Studies of the reaction of 3 with a weaker acid (anisidinium tetrafluoroborate) in acetonitrile indicate that a rapid intermolecular proton exchange interconverts isomers 4a and 4b, and a pKa value of 12 was determined for these two isomers. Protonation of 3 with 2 equiv of triflic acid results in the protonation of both the PNP ligand and the metal hydride to form the dihydrogen complex [(H2)Fe(PNHP) (dmpm)(CH3CN)]3+, 11. Studies of related complexes [HFe(PNP)(dmpm)(CO)]+ (12) and [HFe(depp)(dmpm)(CH 3CN)]+ (10) (where depp is bis(diethylphosphino)propane) confirm the important roles of the pendant base and the ligand trans to the hydride ligand in the rapid intra- and intermolecular hydride/proton exchange reactions observed for 4. Features required for an effective proton relay and their potential relevance to the iron-only hydrogenase enzymes are discussed.

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