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Title: Thermodynamic Hydricities of Biomimetic Organic Hydride Donors

Abstract

Here, thermodynamic hydricities (ΔGH) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me2N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/mol) with the experimental values, obtained using “potential pKa” and “hydride-transfer” methods. The hydride donor abilities of model compounds were in the 48.7–85.8 kcal/mol (acetonitrile) and 46.9–84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydride complexes. To evaluate the relevance of entropic contribution to the overall hydricity, Gibbs free energy differences (ΔGH) obtained in this work were compared with the enthalpy (ΔHH) values obtained by others. The results indicate that, even though ΔHH values exhibit the same trends as ΔGH, the differences between room-temperature ΔGH and ΔHH values range from 3 to 9 kcal/mol. This study also reports a new metal-free hydride donor, namely, an acridine-based compound 3NH, whose hydricity exceeds that of NaBH4. Collectively, this work gives a perspective of use metal-free hydride catalysts in fuel-forming and other reduction processes.

Authors:
 [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Bowling Green State Univ., Bowling Green, OH (United States)
  3. Univ. of Pittsburgh, Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Petroleum Research Fund (PRF); Ohio Supercomputer Center (OSC); Richard King Mellon Foundation; USDOE
OSTI Identifier:
1467646
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 13; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ilic, Stefan, Kadel, Usha Pandey, Basdogan, Yasemin, Keith, John A., and Glusac, Ksenija D.. Thermodynamic Hydricities of Biomimetic Organic Hydride Donors. United States: N. p., 2018. Web. https://doi.org/10.1021/jacs.7b13526.
Ilic, Stefan, Kadel, Usha Pandey, Basdogan, Yasemin, Keith, John A., & Glusac, Ksenija D.. Thermodynamic Hydricities of Biomimetic Organic Hydride Donors. United States. https://doi.org/10.1021/jacs.7b13526
Ilic, Stefan, Kadel, Usha Pandey, Basdogan, Yasemin, Keith, John A., and Glusac, Ksenija D.. Fri . "Thermodynamic Hydricities of Biomimetic Organic Hydride Donors". United States. https://doi.org/10.1021/jacs.7b13526. https://www.osti.gov/servlets/purl/1467646.
@article{osti_1467646,
title = {Thermodynamic Hydricities of Biomimetic Organic Hydride Donors},
author = {Ilic, Stefan and Kadel, Usha Pandey and Basdogan, Yasemin and Keith, John A. and Glusac, Ksenija D.},
abstractNote = {Here, thermodynamic hydricities (ΔGH–) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me2N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/mol) with the experimental values, obtained using “potential pKa” and “hydride-transfer” methods. The hydride donor abilities of model compounds were in the 48.7–85.8 kcal/mol (acetonitrile) and 46.9–84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydride complexes. To evaluate the relevance of entropic contribution to the overall hydricity, Gibbs free energy differences (ΔGH–) obtained in this work were compared with the enthalpy (ΔHH–) values obtained by others. The results indicate that, even though ΔHH– values exhibit the same trends as ΔGH–, the differences between room-temperature ΔGH– and ΔHH– values range from 3 to 9 kcal/mol. This study also reports a new metal-free hydride donor, namely, an acridine-based compound 3NH, whose hydricity exceeds that of NaBH4. Collectively, this work gives a perspective of use metal-free hydride catalysts in fuel-forming and other reduction processes.},
doi = {10.1021/jacs.7b13526},
journal = {Journal of the American Chemical Society},
number = 13,
volume = 140,
place = {United States},
year = {2018},
month = {3}
}

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Figures / Tables:

Scheme 1 Scheme 1: Structure of organic hydrides: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH and CAFH), acridine (Ph-AcrH, Me2N-AcrH, T-AcrH, 4OH, 2OH, 3NH) and triarlymethane (6OH) derivatives.

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