Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes

Rebecca Ciancanelli, Bruce C. Noll, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

114 Citations (Scopus)

Abstract

A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H2Co(dppe)2]+, HCo(dppe)2, [HCo(dppe)2(CH3CN)]+, and [Co(dppe)2-(CH3CN)]2+, where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H2Co(dppe)2]+ and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)2]+ to form [Co(dppe)2]+ and [H2Co(dppe)2]+, the reaction of [Co(dppe)2]+ with H2, the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.

Original languageEnglish
Pages (from-to)2984-2992
Number of pages9
JournalJournal of the American Chemical Society
Volume124
Issue number12
DOIs
Publication statusPublished - Mar 27 2002

Fingerprint

Cobalt
Thermodynamics
Hydrides
Protons
Hydrogen
Hydrogen bonds
Metals
Deprotonation
Proton transfer
Protonation
Ethane
Free energy
bis(diphenylphosphine)ethane
Derivatives

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes. / Ciancanelli, Rebecca; Noll, Bruce C.; DuBois, Daniel L; Rakowski DuBois, M.

In: Journal of the American Chemical Society, Vol. 124, No. 12, 27.03.2002, p. 2984-2992.

Research output: Contribution to journalArticle

@article{9e0e6aa911884727b519fbb9daeb8870,
title = "Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes",
abstract = "A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H2Co(dppe)2]+, HCo(dppe)2, [HCo(dppe)2(CH3CN)]+, and [Co(dppe)2-(CH3CN)]2+, where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H2Co(dppe)2]+ and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)2]+ to form [Co(dppe)2]+ and [H2Co(dppe)2]+, the reaction of [Co(dppe)2]+ with H2, the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.",
author = "Rebecca Ciancanelli and Noll, {Bruce C.} and DuBois, {Daniel L} and {Rakowski DuBois}, M.",
year = "2002",
month = "3",
day = "27",
doi = "10.1021/ja0122804",
language = "English",
volume = "124",
pages = "2984--2992",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes

AU - Ciancanelli, Rebecca

AU - Noll, Bruce C.

AU - DuBois, Daniel L

AU - Rakowski DuBois, M.

PY - 2002/3/27

Y1 - 2002/3/27

N2 - A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H2Co(dppe)2]+, HCo(dppe)2, [HCo(dppe)2(CH3CN)]+, and [Co(dppe)2-(CH3CN)]2+, where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H2Co(dppe)2]+ and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)2]+ to form [Co(dppe)2]+ and [H2Co(dppe)2]+, the reaction of [Co(dppe)2]+ with H2, the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.

AB - A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H2Co(dppe)2]+, HCo(dppe)2, [HCo(dppe)2(CH3CN)]+, and [Co(dppe)2-(CH3CN)]2+, where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H2Co(dppe)2]+ and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)2]+ to form [Co(dppe)2]+ and [H2Co(dppe)2]+, the reaction of [Co(dppe)2]+ with H2, the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.

UR - http://www.scopus.com/inward/record.url?scp=0037181384&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037181384&partnerID=8YFLogxK

U2 - 10.1021/ja0122804

DO - 10.1021/ja0122804

M3 - Article

VL - 124

SP - 2984

EP - 2992

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 12

ER -