Indirect Detection of Short-Lived Hydride Intermediates of Iridium N-Heterocyclic Carbene Complexes via Chemical Exchange Saturation Transfer Spectroscopy

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Indirect Detection of Short-Lived Hydride Intermediates of Iridium N-Heterocyclic Carbene Complexes via Chemical Exchange Saturation Transfer Spectroscopy. / Knecht, Stephan; Hadjiali, Sara; Barskiy, Danila A. et al.

In: Journal of Physical Chemistry C, Vol. 123, No. 26, 07.06.2019, p. 16288-16293.

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

BibTeX

@article{99a2b4d900464a8e86024650ef9ee3c4,

title = "Indirect Detection of Short-Lived Hydride Intermediates of Iridium N-Heterocyclic Carbene Complexes via Chemical Exchange Saturation Transfer Spectroscopy",

abstract = "For the first time, chemical exchange saturation transfer (CEST) nuclear magnetic resonance (NMR) is utilized to study short-lived hydride intermediates in the catalytic cycle of an organometallic complex [Ir(IMes)(Py)3(H)2]Cl. These complexes are typically not observable by other NMR techniques because they are low concentrated and undergo reversible ligand exchange with the main complex. The intermediate complexes [Ir(Cl)(IMes)(Py)2(H)2] and [Ir(CD3OD)(IMes)(Py)2(H)2] are detected, assigned, and characterized in solution, in situ and at room temperature. Understanding the spin dynamics in these complexes is necessary for enhancing the performance of the nuclear spin hyperpolarization technique signal amplification by reversible exchange. By eliminating [Ir(Cl)(IMes)(Py)2(H)2] and manipulating the spin system by radiofrequency irradiation, the nuclear spin singlet lifetime of the hydride protons was increased by more than an order of magnitude, from 2.2 ± 0.1 to 27.2 ± 1.2 s. Because of its simplicity and ability to unravel unobservable chemical species, the utilized CEST NMR approach has a large application potential for studying short-lived hydride intermediates in catalytic reactions.",

keywords = "PARA-HYDROGEN, N-15 HYPERPOLARIZATION, MAGNETIZATION-TRANSFER, NMR DETECTION, SPIN STATES, PARAHYDROGEN, POLARIZATION, SABRE, DECOMPOSITION, CATALYSTS",

author = "Stephan Knecht and Sara Hadjiali and Barskiy, {Danila A.} and Alexander Pines and Grit Sauer and Kiryutin, {Alexey S.} and Ivanov, {Konstantin L.} and Yurkovskaya, {Alexandra V.} and Gerd Buntkowsky",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = jun,

day = "7",

doi = "10.1021/acs.jpcc.9b04179",

language = "English",

volume = "123",

pages = "16288--16293",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "26",

}

RIS

TY - JOUR

T1 - Indirect Detection of Short-Lived Hydride Intermediates of Iridium N-Heterocyclic Carbene Complexes via Chemical Exchange Saturation Transfer Spectroscopy

AU - Knecht, Stephan

AU - Hadjiali, Sara

AU - Barskiy, Danila A.

AU - Pines, Alexander

AU - Sauer, Grit

AU - Kiryutin, Alexey S.

AU - Ivanov, Konstantin L.

AU - Yurkovskaya, Alexandra V.

AU - Buntkowsky, Gerd

PY - 2019/6/7

Y1 - 2019/6/7

N2 - For the first time, chemical exchange saturation transfer (CEST) nuclear magnetic resonance (NMR) is utilized to study short-lived hydride intermediates in the catalytic cycle of an organometallic complex [Ir(IMes)(Py)3(H)2]Cl. These complexes are typically not observable by other NMR techniques because they are low concentrated and undergo reversible ligand exchange with the main complex. The intermediate complexes [Ir(Cl)(IMes)(Py)2(H)2] and [Ir(CD3OD)(IMes)(Py)2(H)2] are detected, assigned, and characterized in solution, in situ and at room temperature. Understanding the spin dynamics in these complexes is necessary for enhancing the performance of the nuclear spin hyperpolarization technique signal amplification by reversible exchange. By eliminating [Ir(Cl)(IMes)(Py)2(H)2] and manipulating the spin system by radiofrequency irradiation, the nuclear spin singlet lifetime of the hydride protons was increased by more than an order of magnitude, from 2.2 ± 0.1 to 27.2 ± 1.2 s. Because of its simplicity and ability to unravel unobservable chemical species, the utilized CEST NMR approach has a large application potential for studying short-lived hydride intermediates in catalytic reactions.

AB - For the first time, chemical exchange saturation transfer (CEST) nuclear magnetic resonance (NMR) is utilized to study short-lived hydride intermediates in the catalytic cycle of an organometallic complex [Ir(IMes)(Py)3(H)2]Cl. These complexes are typically not observable by other NMR techniques because they are low concentrated and undergo reversible ligand exchange with the main complex. The intermediate complexes [Ir(Cl)(IMes)(Py)2(H)2] and [Ir(CD3OD)(IMes)(Py)2(H)2] are detected, assigned, and characterized in solution, in situ and at room temperature. Understanding the spin dynamics in these complexes is necessary for enhancing the performance of the nuclear spin hyperpolarization technique signal amplification by reversible exchange. By eliminating [Ir(Cl)(IMes)(Py)2(H)2] and manipulating the spin system by radiofrequency irradiation, the nuclear spin singlet lifetime of the hydride protons was increased by more than an order of magnitude, from 2.2 ± 0.1 to 27.2 ± 1.2 s. Because of its simplicity and ability to unravel unobservable chemical species, the utilized CEST NMR approach has a large application potential for studying short-lived hydride intermediates in catalytic reactions.

KW - PARA-HYDROGEN

KW - N-15 HYPERPOLARIZATION

KW - MAGNETIZATION-TRANSFER

KW - NMR DETECTION

KW - SPIN STATES

KW - PARAHYDROGEN

KW - POLARIZATION

KW - SABRE

KW - DECOMPOSITION

KW - CATALYSTS

UR - http://www.scopus.com/inward/record.url?scp=85070333787&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b04179

DO - 10.1021/acs.jpcc.9b04179

M3 - Article

AN - SCOPUS:85070333787

VL - 123

SP - 16288

EP - 16293

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 26

ER -

ID: 21239707