Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes

William W. Ellis, Alex Miedaner, Calvin J. Curtis, Dorothy H. Gibson, Daniel L DuBois

Research output: Contribution to journal › Article

68 Citations (Scopus)

Abstract

The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO) (CHO). From the equilibrium constant for the hydride transfer (16.2), the ΔG° for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating donating ability, ΔG°H-, is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) → M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E1/2(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known ΔG°H- values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.

Original languageEnglish
Pages (from-to)1926-1932
Number of pages7
JournalJournal of the American Chemical Society
Volume124
Issue number9
DOIs
Publication statusPublished - Mar 6 2002

Fingerprint

Rhenium
Coordination Complexes
Metal complexes
Hydrides
Free energy
Transition metals
Ethane
Porifera
Protons
Hydrogen
Ions
Equilibrium constants
Cyclic voltammetry
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes. / Ellis, William W.; Miedaner, Alex; Curtis, Calvin J.; Gibson, Dorothy H.; DuBois, Daniel L.

In: Journal of the American Chemical Society, Vol. 124, No. 9, 06.03.2002, p. 1926-1932.

Research output: Contribution to journal › Article

Ellis, WW, Miedaner, A, Curtis, CJ, Gibson, DH & DuBois, DL 2002, 'Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes', Journal of the American Chemical Society, vol. 124, no. 9, pp. 1926-1932. https://doi.org/10.1021/ja0116831
Ellis WW, Miedaner A, Curtis CJ, Gibson DH, DuBois DL. Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes. Journal of the American Chemical Society. 2002 Mar 6;124(9):1926-1932. https://doi.org/10.1021/ja0116831
Ellis, William W. ; Miedaner, Alex ; Curtis, Calvin J. ; Gibson, Dorothy H. ; DuBois, Daniel L. / Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 9. pp. 1926-1932.
@article{6b84843f4cf84d4baabd6e3bc8ff05d7,
title = "Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes",
abstract = "The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO) (CHO). From the equilibrium constant for the hydride transfer (16.2), the ΔG° for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating donating ability, ΔG°H-, is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) → M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E1/2(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known ΔG°H- values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.",
author = "Ellis, {William W.} and Alex Miedaner and Curtis, {Calvin J.} and Gibson, {Dorothy H.} and DuBois, {Daniel L}",
year = "2002",
month = "3",
day = "6",
doi = "10.1021/ja0116831",
language = "English",
volume = "124",
pages = "1926--1932",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Hydride donor abilities and bond dissociation free energies of transition metal formyl complexes

AU - Ellis, William W.

AU - Miedaner, Alex

AU - Curtis, Calvin J.

AU - Gibson, Dorothy H.

AU - DuBois, Daniel L

PY - 2002/3/6

Y1 - 2002/3/6

N2 - The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO) (CHO). From the equilibrium constant for the hydride transfer (16.2), the ΔG° for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating donating ability, ΔG°H-, is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) → M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E1/2(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known ΔG°H- values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.

AB - The hydride complex [Pt(dmpe)2H]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) reversibly transfers H- to the rhenium carbonyl complex [CpRe(PMe3)(NO)(CO)]+, giving the formyl CpRe(PMe3)(NO) (CHO). From the equilibrium constant for the hydride transfer (16.2), the ΔG° for the reaction was determined (-1.6 kcal/mol), as was the hydride-donating ability of the formyl (44.1 kcal/mol). The hydride-donating donating ability, ΔG°H-, is defined as the energy required to release the hydride ion into solution by the formyl complex [i.e. M(CHO) → M(CO)+ + H-]. Subsequently, the hydride-donating ability of a series of formyl complexes was determined, ranging from 44 to 55 kcal/mol. With use of this information, two rhenium carbonyl complexes, [CpRe(NO)(CO)2]+and [Cp*Re(NO)(CO)2]+, were hydrogenated to formyls, employing [Pt(dmpp)2]2+ and Proton-Sponge. Finally, the E1/2(I/0) values for five rhenium carbonyl complexes were measured by cyclic voltammetry. Combined with the known ΔG°H- values for the complexes, the hydrogen atom donating abilities could be determined. These values were all found to be approximately 50 kcal/mol.

UR - http://www.scopus.com/inward/record.url?scp=0037029009&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037029009&partnerID=8YFLogxK

U2 - 10.1021/ja0116831

DO - 10.1021/ja0116831

M3 - Article

VL - 124

SP - 1926

EP - 1932

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 9

ER -

Access to Document