Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy

Lydia E. Nodaraki; Jingjing Liu; Ana-Maria Ariciu; Fabrizio Ortu; Meagan S. Oakley; Letitia Birnoschi; Gemma K. Gransbury; Philip J. Cobb; Jack Emerson-King; Nicholas F. Chilton; David P. Mills; Eric J. L. McInnes; Floriana Tuna

doi:10.1039/d3sc06175b

Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy

Lydia E. Nodaraki, Jingjing Liu, Ana-Maria Ariciu, Fabrizio Ortu, Meagan S. Oakley, Letitia Birnoschi, Gemma K. Gransbury, Philip J. Cobb, Jack Emerson-King, Nicholas F. Chilton^*, David P. Mills^*, Eric J. L. McInnes^*, Floriana Tuna^*

^*Corresponding author for this work

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

5 Citations (Scopus)

Abstract

We examine lanthanide (Ln)-ligand bonding in a family of early Ln ³⁺ complexes [Ln(Cp ^tt) ₃] (1-Ln, Ln = La, Ce, Nd, Sm; Cp ^tt = C ₅H ₃ ^tBu ₂-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T ₁ and T _m relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1-Sm), respectively, at 5 K: the T ₁ relaxation of 1-Nd is more than 10 ² times faster than its valence isoelectronic uranium analogue. ¹³C and ¹H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.

Original language	English
Pages (from-to)	3003-3010
Number of pages	8
Journal	Chemical Science
Volume	15
Issue number	8
Early online date	16 Jan 2024
DOIs	https://doi.org/10.1039/d3sc06175b
Publication status	Published - 22 Feb 2024
Externally published	Yes

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Nodaraki, L. E., Liu, J., Ariciu, A.-M., Ortu, F., Oakley, M. S., Birnoschi, L., Gransbury, G. K., Cobb, P. J., Emerson-King, J., Chilton, N. F., Mills, D. P., McInnes, E. J. L., & Tuna, F. (2024). Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy. Chemical Science, 15(8), 3003-3010. https://doi.org/10.1039/d3sc06175b

@article{495e725ae29543b09d892ca9162326d5,

title = "Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy",

abstract = "We examine lanthanide (Ln)-ligand bonding in a family of early Ln 3+ complexes [Ln(Cp tt) 3] (1-Ln, Ln = La, Ce, Nd, Sm; Cp tt = C 5H 3 tBu 2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T 1 and T m relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1-Sm), respectively, at 5 K: the T 1 relaxation of 1-Nd is more than 10 2 times faster than its valence isoelectronic uranium analogue. 13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.",

keywords = "Chemistry, Coherence, Covalency, Electronic-structure, Ligands, Molecular qubits, Paramagnetic-resonance, Reactivity, Spin relaxation, Tris(eta-5-cyclopentadienyl) actinide complexes",

author = "Nodaraki, {Lydia E.} and Jingjing Liu and Ana-Maria Ariciu and Fabrizio Ortu and Oakley, {Meagan S.} and Letitia Birnoschi and Gransbury, {Gemma K.} and Cobb, {Philip J.} and Jack Emerson-King and Chilton, {Nicholas F.} and Mills, {David P.} and McInnes, {Eric J. L.} and Floriana Tuna",

note = "Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

month = feb,

day = "22",

doi = "10.1039/d3sc06175b",

language = "English",

volume = "15",

pages = "3003--3010",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy

AU - Nodaraki, Lydia E.

AU - Liu, Jingjing

AU - Ariciu, Ana-Maria

AU - Ortu, Fabrizio

AU - Oakley, Meagan S.

AU - Birnoschi, Letitia

AU - Gransbury, Gemma K.

AU - Cobb, Philip J.

AU - Emerson-King, Jack

AU - Chilton, Nicholas F.

AU - Mills, David P.

AU - McInnes, Eric J. L.

AU - Tuna, Floriana

PY - 2024/2/22

Y1 - 2024/2/22

N2 - We examine lanthanide (Ln)-ligand bonding in a family of early Ln 3+ complexes [Ln(Cp tt) 3] (1-Ln, Ln = La, Ce, Nd, Sm; Cp tt = C 5H 3 tBu 2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T 1 and T m relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1-Sm), respectively, at 5 K: the T 1 relaxation of 1-Nd is more than 10 2 times faster than its valence isoelectronic uranium analogue. 13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.

AB - We examine lanthanide (Ln)-ligand bonding in a family of early Ln 3+ complexes [Ln(Cp tt) 3] (1-Ln, Ln = La, Ce, Nd, Sm; Cp tt = C 5H 3 tBu 2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin T 1 and T m relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.7 μs (1-Sm), respectively, at 5 K: the T 1 relaxation of 1-Nd is more than 10 2 times faster than its valence isoelectronic uranium analogue. 13C and 1H hyperfine sublevel correlation (HYSCORE) spectroscopy reveals that the extent of covalency is negligible in these Ln compounds, with much smaller hyperfine interactions than observed for equivalent actinide (Th and U) complexes. This is corroborated by ab initio calculations, confirming the predominant electrostatic nature of the metal-ligand bonding in these complexes.

KW - Chemistry

KW - Coherence

KW - Covalency

KW - Electronic-structure

KW - Ligands

KW - Molecular qubits

KW - Paramagnetic-resonance

KW - Reactivity

KW - Spin relaxation

KW - Tris(eta-5-cyclopentadienyl) actinide complexes

UR - http://www.scopus.com/inward/record.url?scp=85183499789&partnerID=8YFLogxK

U2 - 10.1039/d3sc06175b

DO - 10.1039/d3sc06175b

M3 - Article

SN - 2041-6520

VL - 15

SP - 3003

EP - 3010

JO - Chemical Science

JF - Chemical Science

IS - 8

ER -

Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy

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