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 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 Chilton, David P. Mills, Eric J. L. Mcinnes, Floriana Tuna

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Abstract

We examine lanthanide (Ln)-ligand bonding in a family of early Ln³⁺ complexes [Ln(Cp^tt)₃] (1-Ln, Ln = La, Ce, Nd, Sm; Cp^tt = C₅H₃^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 T1 and Tm 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 T₁ relaxation of 1-Nd is more than 10² times faster than its valence isolelectronic 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
Journal	Chemical Science
Issue number	8
DOIs	https://doi.org/10.1039/D3SC06175B
Publication status	Accepted/In press - 12 Jan 2024

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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., Mills, D. P., Mcinnes, E. J. L., & Tuna, F. (Accepted/In press). Metal-carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy. Chemical Science, (8). https://doi.org/10.1039/D3SC06175B

@article{a85eaa28ce254370b848639feba25ab6,

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 Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) 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 T1 and Tm 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 T1 relaxation of 1-Nd is more than 102 times faster than its valence isolelectronic 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.",

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 Nicholas Chilton and Mills, {David P.} and Mcinnes, {Eric J. L.} and Floriana Tuna",

year = "2024",

month = jan,

day = "12",

doi = "10.1039/D3SC06175B",

language = "English",

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

AU - Mills, David P.

AU - Mcinnes, Eric J. L.

AU - Tuna, Floriana

PY - 2024/1/12

Y1 - 2024/1/12

N2 - We examine lanthanide (Ln)-ligand bonding in a family of early Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) 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 T1 and Tm 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 T1 relaxation of 1-Nd is more than 102 times faster than its valence isolelectronic 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 Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) 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 T1 and Tm 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 T1 relaxation of 1-Nd is more than 102 times faster than its valence isolelectronic 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.

U2 - 10.1039/D3SC06175B

DO - 10.1039/D3SC06175B

M3 - Article

SN - 2041-6520

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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