Free energy landscapes for S-H bonds in Cp* 2Mo 2S 4 complexes

Aaron Appel, Suh Jane Lee, James A. Franz, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(μ-S) 2(μ-SMe)(μ-SH)MoCp * and Cp*Mo(μ-S) 2(μ-SH) 2MoCp*. These data include electrochemical potentials, pK a values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp 2 +/o for electrochemical potentials, 5 to 31 for pK a values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The extensive set of thermochemical data is presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under varying conditions of pH and H 2 overpressure. In addition to the previously studied homogeneous reactivity and catalysis, Mo 2S 4 complexes are also models for heterogeneous molybdenum sulfide catalysts, and therefore, the present results demonstrate the dramatic range of S-H bond strengths available in both homogeneous and heterogeneous reaction pathways.

Original languageEnglish
Pages (from-to)5224-5232
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number14
DOIs
Publication statusPublished - Apr 15 2009

Fingerprint

Hydrides
Free energy
Catalysis
Thermodynamics
Metals
Acetonitrile
Molybdenum
Transition metals
Catalysts
Datasets
molybdenum disulfide
acetonitrile
Sulfides

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry
  • Medicine(all)

Cite this

Free energy landscapes for S-H bonds in Cp* 2Mo 2S 4 complexes. / Appel, Aaron; Lee, Suh Jane; Franz, James A.; DuBois, Daniel L; DuBois, M. Rakowski.

In: Journal of the American Chemical Society, Vol. 131, No. 14, 15.04.2009, p. 5224-5232.

Research output: Contribution to journalArticle

Appel, Aaron ; Lee, Suh Jane ; Franz, James A. ; DuBois, Daniel L ; DuBois, M. Rakowski. / Free energy landscapes for S-H bonds in Cp* 2Mo 2S 4 complexes. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 14. pp. 5224-5232.
@article{095965c031834d52af761f050e140f27,
title = "Free energy landscapes for S-H bonds in Cp* 2Mo 2S 4 complexes",
abstract = "An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(μ-S) 2(μ-SMe)(μ-SH)MoCp * and Cp*Mo(μ-S) 2(μ-SH) 2MoCp*. These data include electrochemical potentials, pK a values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp 2 +/o for electrochemical potentials, 5 to 31 for pK a values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The extensive set of thermochemical data is presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under varying conditions of pH and H 2 overpressure. In addition to the previously studied homogeneous reactivity and catalysis, Mo 2S 4 complexes are also models for heterogeneous molybdenum sulfide catalysts, and therefore, the present results demonstrate the dramatic range of S-H bond strengths available in both homogeneous and heterogeneous reaction pathways.",
author = "Aaron Appel and Lee, {Suh Jane} and Franz, {James A.} and DuBois, {Daniel L} and DuBois, {M. Rakowski}",
year = "2009",
month = "4",
day = "15",
doi = "10.1021/ja8093179",
language = "English",
volume = "131",
pages = "5224--5232",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Free energy landscapes for S-H bonds in Cp* 2Mo 2S 4 complexes

AU - Appel, Aaron

AU - Lee, Suh Jane

AU - Franz, James A.

AU - DuBois, Daniel L

AU - DuBois, M. Rakowski

PY - 2009/4/15

Y1 - 2009/4/15

N2 - An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(μ-S) 2(μ-SMe)(μ-SH)MoCp * and Cp*Mo(μ-S) 2(μ-SH) 2MoCp*. These data include electrochemical potentials, pK a values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp 2 +/o for electrochemical potentials, 5 to 31 for pK a values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The extensive set of thermochemical data is presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under varying conditions of pH and H 2 overpressure. In addition to the previously studied homogeneous reactivity and catalysis, Mo 2S 4 complexes are also models for heterogeneous molybdenum sulfide catalysts, and therefore, the present results demonstrate the dramatic range of S-H bond strengths available in both homogeneous and heterogeneous reaction pathways.

AB - An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(μ-S) 2(μ-SMe)(μ-SH)MoCp * and Cp*Mo(μ-S) 2(μ-SH) 2MoCp*. These data include electrochemical potentials, pK a values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp 2 +/o for electrochemical potentials, 5 to 31 for pK a values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The extensive set of thermochemical data is presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under varying conditions of pH and H 2 overpressure. In addition to the previously studied homogeneous reactivity and catalysis, Mo 2S 4 complexes are also models for heterogeneous molybdenum sulfide catalysts, and therefore, the present results demonstrate the dramatic range of S-H bond strengths available in both homogeneous and heterogeneous reaction pathways.

UR - http://www.scopus.com/inward/record.url?scp=67949088114&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67949088114&partnerID=8YFLogxK

U2 - 10.1021/ja8093179

DO - 10.1021/ja8093179

M3 - Article

VL - 131

SP - 5224

EP - 5232

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 14

ER -