Theoretical Characterization of Bis(pentaisopropylcyclopentadienyl) Rare-Earth Metallocenes DOI
Ahmadreza Rajabi, Dang Khoa Nguyen, Robin Grotjahn

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

We report ground states, equilibrium structures, and both electronic electron paramagnetic resonance (EPR) spectra of divalent rare-earth metallocenes Ln(CpiPr5)2 as obtained from scalar exact two-component (X2C) relativistic density functional theory (DFT) calculations. While the results for with Ln = Nd, Sm, Eu, Tm, Yb are consistent a conventional (4f)n+1 configuration metal atom, La, Ce, Gd, Lu best described having (4f)n(5d)1 states. Strong mixing is observed Pr; Ho Er, two distinct states character energetically close, comparison available experimental data slightly favors ground-state assignment. Our show that Nd Pr compounds have strong or partial character, suggesting previous assignments based solely on atomic f-d splittings [McClain, K. R. J. Am. Chem. Soc. 2022, 144, 22193-22201. 10.1021/jacs.2c09880] should be revised. X2C calculations EPR parameters magnitude isotropic hyperfine coupling (HFC) relative to an reference poor descriptor s/d mixing, this approach unreliable compounds. A massive HFC constant 4401 MHz predicted compound.

Language: Английский

Theoretical Characterization of Bis(pentaisopropylcyclopentadienyl) Rare-Earth Metallocenes DOI
Ahmadreza Rajabi, Dang Khoa Nguyen, Robin Grotjahn

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

We report ground states, equilibrium structures, and both electronic electron paramagnetic resonance (EPR) spectra of divalent rare-earth metallocenes Ln(CpiPr5)2 as obtained from scalar exact two-component (X2C) relativistic density functional theory (DFT) calculations. While the results for with Ln = Nd, Sm, Eu, Tm, Yb are consistent a conventional (4f)n+1 configuration metal atom, La, Ce, Gd, Lu best described having (4f)n(5d)1 states. Strong mixing is observed Pr; Ho Er, two distinct states character energetically close, comparison available experimental data slightly favors ground-state assignment. Our show that Nd Pr compounds have strong or partial character, suggesting previous assignments based solely on atomic f-d splittings [McClain, K. R. J. Am. Chem. Soc. 2022, 144, 22193-22201. 10.1021/jacs.2c09880] should be revised. X2C calculations EPR parameters magnitude isotropic hyperfine coupling (HFC) relative to an reference poor descriptor s/d mixing, this approach unreliable compounds. A massive HFC constant 4401 MHz predicted compound.

Language: Английский

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