Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts

Neeraj Kumar, Jonathan M. Darmon, Charles J. Weiss, Monte Helm, Simone Raugei, R Morris Bullock

Research output: Contribution to journalArticle

Abstract

The intra- and intermolecular deprotonation reactions of [(Cp C 5 F 4 N )Fe(P Et N R P Et )H] + (P Et N R P Et = (Et 2 PCH 2 ) 2 NR′) complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R′ = Me, Et, CH 2 OMe, CH 2 N(Ph)Me, and (CH 2 ) n NMe 2 ; n = 1-4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen-bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(Cp C 5 F 4 N )Fe(P Et N R P Et )H] + (R′ = (CH 2 ) 3 NMe 2 ) electrocatalyst was predicted to have the most favorable free energy (ΔG) and free energy of activation (ΔG ). To verify the computational results, two of the iron precatalysts, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) n NMe 2 P Et )Cl (n = 2 and 4), were synthesized, and their electrocatalytic activity for the oxidation of hydrogen was determined under an atmosphere of H 2 using DABCO as the exogenous base. Maximum turnover frequencies of 270 and 200 s -1 were measured when n = 2 and 4, respectively, validating the computational results.

Original languageEnglish
Pages (from-to)1391-1396
Number of pages6
JournalOrganometallics
Volume38
Issue number6
DOIs
Publication statusPublished - Mar 25 2019

Fingerprint

Deprotonation
electrocatalysts
Electrocatalysts
relay
Protons
Hydrogen
Iron
methylidyne
iron
Oxidation
oxidation
protons
hydrogen
Free energy
Atoms
free energy
Hydrides
Amines
Density functional theory
Hydrogen bonds

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts. / Kumar, Neeraj; Darmon, Jonathan M.; Weiss, Charles J.; Helm, Monte; Raugei, Simone; Bullock, R Morris.

In: Organometallics, Vol. 38, No. 6, 25.03.2019, p. 1391-1396.

Research output: Contribution to journalArticle

@article{76db2fb866484edaa1ec281c0d074e06,
title = "Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts",
abstract = "The intra- and intermolecular deprotonation reactions of [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (P Et N R ′ P Et = (Et 2 PCH 2 ) 2 NR′) complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R′ = Me, Et, CH 2 OMe, CH 2 N(Ph)Me, and (CH 2 ) n NMe 2 ; n = 1-4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen-bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (R′ = (CH 2 ) 3 NMe 2 ) electrocatalyst was predicted to have the most favorable free energy (ΔG) and free energy of activation (ΔG ∂ ). To verify the computational results, two of the iron precatalysts, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) n NMe 2 P Et )Cl (n = 2 and 4), were synthesized, and their electrocatalytic activity for the oxidation of hydrogen was determined under an atmosphere of H 2 using DABCO as the exogenous base. Maximum turnover frequencies of 270 and 200 s -1 were measured when n = 2 and 4, respectively, validating the computational results.",
author = "Neeraj Kumar and Darmon, {Jonathan M.} and Weiss, {Charles J.} and Monte Helm and Simone Raugei and Bullock, {R Morris}",
year = "2019",
month = "3",
day = "25",
doi = "10.1021/acs.organomet.8b00805",
language = "English",
volume = "38",
pages = "1391--1396",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Outer Coordination Sphere Proton Relay Base and Proximity Effects on Hydrogen Oxidation with Iron Electrocatalysts

AU - Kumar, Neeraj

AU - Darmon, Jonathan M.

AU - Weiss, Charles J.

AU - Helm, Monte

AU - Raugei, Simone

AU - Bullock, R Morris

PY - 2019/3/25

Y1 - 2019/3/25

N2 - The intra- and intermolecular deprotonation reactions of [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (P Et N R ′ P Et = (Et 2 PCH 2 ) 2 NR′) complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R′ = Me, Et, CH 2 OMe, CH 2 N(Ph)Me, and (CH 2 ) n NMe 2 ; n = 1-4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen-bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (R′ = (CH 2 ) 3 NMe 2 ) electrocatalyst was predicted to have the most favorable free energy (ΔG) and free energy of activation (ΔG ∂ ). To verify the computational results, two of the iron precatalysts, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) n NMe 2 P Et )Cl (n = 2 and 4), were synthesized, and their electrocatalytic activity for the oxidation of hydrogen was determined under an atmosphere of H 2 using DABCO as the exogenous base. Maximum turnover frequencies of 270 and 200 s -1 were measured when n = 2 and 4, respectively, validating the computational results.

AB - The intra- and intermolecular deprotonation reactions of [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (P Et N R ′ P Et = (Et 2 PCH 2 ) 2 NR′) complexes are rate-limiting processes in the electrocatalytic oxidation of hydrogen and can be mediated by an amine base in the outer coordination sphere (OCS) by facilitating the matching of energy of deprotonation intermediates. A series of complexes with different N-substituents (R′ = Me, Et, CH 2 OMe, CH 2 N(Ph)Me, and (CH 2 ) n NMe 2 ; n = 1-4) was examined computationally using density functional theory to determine the influence of the identity and proximity of the OCS base on the intramolecular deprotonation. Complexes with an OCS dimethylamino substituent were the most suitably energy matched. The number of carbon atoms between the secondary and OCS nitrogen atoms dictated the strength of the hydrogen-bonding interaction and ring strain following deprotonation of the iron hydride. The previously reported [(Cp C 5 F 4 N )Fe(P Et N R ′ P Et )H] + (R′ = (CH 2 ) 3 NMe 2 ) electrocatalyst was predicted to have the most favorable free energy (ΔG) and free energy of activation (ΔG ∂ ). To verify the computational results, two of the iron precatalysts, (Cp C 5 F 4 N )Fe(P Et N (CH 2 ) n NMe 2 P Et )Cl (n = 2 and 4), were synthesized, and their electrocatalytic activity for the oxidation of hydrogen was determined under an atmosphere of H 2 using DABCO as the exogenous base. Maximum turnover frequencies of 270 and 200 s -1 were measured when n = 2 and 4, respectively, validating the computational results.

UR - http://www.scopus.com/inward/record.url?scp=85063340462&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85063340462&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.8b00805

DO - 10.1021/acs.organomet.8b00805

M3 - Article

VL - 38

SP - 1391

EP - 1396

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 6

ER -