Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex

Xiaochen Cai; Subhojit Majumdar; George Charles Fortman; Catherine S.J. Cazin; Alexandra Martha Zoya Slawin; Charles Lhermitte; Rajeev Prabhakar; Meaghan E. Germain; Taryn Palluccio; Steven Patrick Nolan; Elena V. Rybak-Akimova; Manuel Temprado; Burjor Captain; Carl D. Hoff

doi:10.1021/ja1103348

Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR₃, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)₂(η¹-O₂)₂] Complex

Xiaochen Cai, Subhojit Majumdar, George Charles Fortman, Catherine S.J. Cazin, Alexandra Martha Zoya Slawin, Charles Lhermitte, Rajeev Prabhakar, Meaghan E. Germain, Taryn Palluccio, Steven Patrick Nolan, Elena V. Rybak-Akimova, Manuel Temprado, Burjor Captain, Carl D. Hoff

Research output: Contribution to journal › Article › peer-review

Abstract

The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.

Original language	English
Pages (from-to)	1290-1293
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	5
DOIs	https://doi.org/10.1021/ja1103348
Publication status	Published - 9 Feb 2011

Keywords

MOLECULAR-OXYGEN
ORGANIC-CHEMICALS
PHOSPHINE-LIGANDS
AEROBIC OXIDATION
HYDRIDE BOND
DIOXYGEN
CATALYSIS
SYSTEM
PEROXO
HYDROPEROXIDE

Access to Document

10.1021/ja1103348

Studies of homogeneous catalysts: Mechanistic studies of homogeneous catalysts
Cazin, C. S. J. (PI)
The Royal Society
6/03/11 → 5/02/12
Project: Standard
Synergistic Ligand Effects in Palladium: Synergistic Ligand Effects in Palladium Catalysis
Cazin, C. S. J. (PI)
EPSRC
13/11/09 → 12/11/10
Project: Standard

Cite this

Cai, X., Majumdar, S., Fortman, G. C., Cazin, C. S. J., Slawin, A. M. Z., Lhermitte, C., Prabhakar, R., Germain, M. E., Palluccio, T., Nolan, S. P., Rybak-Akimova, E. V., Temprado, M., Captain, B., & Hoff, C. D. (2011). Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR₃, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)₂(η¹-O₂)₂] Complex. Journal of the American Chemical Society, 133(5), 1290-1293. https://doi.org/10.1021/ja1103348

@article{ea472d08de5d42e8a661eb45aea23fc9,

title = "Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex",

abstract = "The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.",

keywords = "MOLECULAR-OXYGEN, ORGANIC-CHEMICALS, PHOSPHINE-LIGANDS, AEROBIC OXIDATION, HYDRIDE BOND, DIOXYGEN, CATALYSIS, SYSTEM, PEROXO, HYDROPEROXIDE",

author = "Xiaochen Cai and Subhojit Majumdar and Fortman, {George Charles} and Cazin, {Catherine S.J.} and Slawin, {Alexandra Martha Zoya} and Charles Lhermitte and Rajeev Prabhakar and Germain, {Meaghan E.} and Taryn Palluccio and Nolan, {Steven Patrick} and Rybak-Akimova, {Elena V.} and Manuel Temprado and Burjor Captain and Hoff, {Carl D.}",

year = "2011",

month = feb,

day = "9",

doi = "10.1021/ja1103348",

language = "English",

volume = "133",

pages = "1290--1293",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "5",

}

Cai, X, Majumdar, S, Fortman, GC, Cazin, CSJ, Slawin, AMZ, Lhermitte, C, Prabhakar, R, Germain, ME, Palluccio, T, Nolan, SP, Rybak-Akimova, EV, Temprado, M, Captain, B & Hoff, CD 2011, 'Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR₃, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)₂(η¹-O₂)₂] Complex', Journal of the American Chemical Society, vol. 133, no. 5, pp. 1290-1293. https://doi.org/10.1021/ja1103348

Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR₃, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)₂(η¹-O₂)₂] Complex. / Cai, Xiaochen; Majumdar, Subhojit; Fortman, George Charles et al.
In: Journal of the American Chemical Society, Vol. 133, No. 5, 09.02.2011, p. 1290-1293.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex

AU - Cai, Xiaochen

AU - Majumdar, Subhojit

AU - Fortman, George Charles

AU - Cazin, Catherine S.J.

AU - Slawin, Alexandra Martha Zoya

AU - Lhermitte, Charles

AU - Prabhakar, Rajeev

AU - Germain, Meaghan E.

AU - Palluccio, Taryn

AU - Nolan, Steven Patrick

AU - Rybak-Akimova, Elena V.

AU - Temprado, Manuel

AU - Captain, Burjor

AU - Hoff, Carl D.

PY - 2011/2/9

Y1 - 2011/2/9

N2 - The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.

AB - The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.

KW - MOLECULAR-OXYGEN

KW - ORGANIC-CHEMICALS

KW - PHOSPHINE-LIGANDS

KW - AEROBIC OXIDATION

KW - HYDRIDE BOND

KW - DIOXYGEN

KW - CATALYSIS

KW - SYSTEM

KW - PEROXO

KW - HYDROPEROXIDE

U2 - 10.1021/ja1103348

DO - 10.1021/ja1103348

M3 - Article

SN - 0002-7863

VL - 133

SP - 1290

EP - 1293

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 5

ER -

Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex

Abstract

Keywords

Access to Document

Fingerprint

Projects

Studies of homogeneous catalysts: Mechanistic studies of homogeneous catalysts

Synergistic Ligand Effects in Palladium: Synergistic Ligand Effects in Palladium Catalysis

Cite this

Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR₃, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)₂(η¹-O₂)₂] Complex