Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**

Jingjing Liu; Lydia E. Nodaraki; Daniel O. T. A. Martins; Marcus J. Giansiracusa; Philip J. Cobb; Jack Emerson-King; Fabrizio Ortu; George F. S. Whitehead; Gemma K. Gransbury; Eric J. L. McInnes; Floriana Tuna; David P. Mills

doi:10.1002/ejic.202300552

Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**

Jingjing Liu, Lydia E. Nodaraki, Daniel O. T. A. Martins, Marcus J. Giansiracusa, Philip J. Cobb, Jack Emerson-King, Fabrizio Ortu, George F. S. Whitehead, Gemma K. Gransbury, Eric J. L. McInnes, Floriana Tuna, David P. Mills

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

4 Downloads (Pure)

Abstract

We report the synthesis of a series of temperature-sensitive non-classical early Ln(II) (Ln = lanthanide) complexes, [K(2.2.2-cryptand)][Ln(Cp^tt)₃] (Cp^tt = C₅H₃^tBu₂-1,3; 1-Ln; Ln = La-Nd). Complexes 1-Ln were typically prepared using Schlenk line techniques rather than more common glove box protocols, by the reduction of the parent Ln(III) complexes [Ln(Cp^tt)₃] (2-Ln) with KC₈ in THF in the presence of 2.2.2-cryptand at –30 °C. The majority of the 2-Ln series have been reported previously by the salt metathesis reactions of 3 eq. KCp^tt with parent LnCl₃, and these methods were adapted here to afford 2-Pr. Complexes 1-Ln and 2-Pr were characterized by single crystal XRD, elemental analysis, ATR-IR and UV-Vis-NIR spectroscopy; 1-La and 2-Pr were additionally characterized by c.w. EPR spectroscopy, and variable temperature magnetic susceptibility measurements were performed on 2-Pr. During attempts to synthesize 2-Nd and 2-Sm we also obtained small crops of crystals of [Nd(Cp^tt)₂(μ-I)]₂ (3) and [Sm(Cp^tt)₂(μ Cl)]₂·C₇H₈(4·C₇H₈), respectively; these complexes were also structurally authenticated. The combination of data obtained indicate that the Ln(II) centers in 1-Ln adopt 4fⁿ5d¹electron configurations, in common with other literature examples of [Ln(Cp^R)₃]^–anions (Cp^R = substituted cyclopentadienyl) for these metals.

Original language	English
Article number	e202300552
Journal	European Journal of Inorganic Chemistry
Volume	26
Issue number	36
Early online date	5 Oct 2023
DOIs	https://doi.org/10.1002/ejic.202300552
Publication status	Published - 20 Dec 2023

Keywords

cyclopentadienyl ligands
EPR spectroscopy
lanthanides
low oxidation state
synthetic methods

Access to Document

10.1002/ejic.202300552Licence: CC BY

Cite this

Liu, J., Nodaraki, L. E., Martins, D. O. T. A., Giansiracusa, M. J., Cobb, P. J., Emerson-King, J., Ortu, F., Whitehead, G. F. S., Gransbury, G. K., McInnes, E. J. L., Tuna, F., & Mills, D. P. (2023). Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**. European Journal of Inorganic Chemistry, 26(36), Article e202300552. https://doi.org/10.1002/ejic.202300552

@article{b556f2a9e0d64be0ba25025a0a3642f1,

title = "Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**",

abstract = "We report the synthesis of a series of temperature-sensitive non-classical early Ln(II) (Ln = lanthanide) complexes, [K(2.2.2-cryptand)][Ln(Cptt)3] (Cptt = C5H3tBu2-1,3; 1-Ln; Ln = La-Nd). Complexes 1-Ln were typically prepared using Schlenk line techniques rather than more common glove box protocols, by the reduction of the parent Ln(III) complexes [Ln(Cptt)3] (2-Ln) with KC8 in THF in the presence of 2.2.2-cryptand at –30 °C. The majority of the 2-Ln series have been reported previously by the salt metathesis reactions of 3 eq. KCptt with parent LnCl3, and these methods were adapted here to afford 2-Pr. Complexes 1-Ln and 2-Pr were characterized by single crystal XRD, elemental analysis, ATR-IR and UV-Vis-NIR spectroscopy; 1-La and 2-Pr were additionally characterized by c.w. EPR spectroscopy, and variable temperature magnetic susceptibility measurements were performed on 2-Pr. During attempts to synthesize 2-Nd and 2-Sm we also obtained small crops of crystals of [Nd(Cptt)2(μ-I)]2 (3) and [Sm(Cptt)2(μ Cl)]2·C7H8 (4·C7H8), respectively; these complexes were also structurally authenticated. The combination of data obtained indicate that the Ln(II) centers in 1-Ln adopt 4fn5d1electron configurations, in common with other literature examples of [Ln(CpR)3]–anions (CpR = substituted cyclopentadienyl) for these metals.",

keywords = "cyclopentadienyl ligands, EPR spectroscopy, lanthanides, low oxidation state, synthetic methods",

author = "Jingjing Liu and Nodaraki, {Lydia E.} and Martins, {Daniel O. T. A.} and Giansiracusa, {Marcus J.} and Cobb, {Philip J.} and Jack Emerson-King and Fabrizio Ortu and Whitehead, {George F. S.} and Gransbury, {Gemma K.} and McInnes, {Eric J. L.} and Floriana Tuna and Mills, {David P.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.",

year = "2023",

month = dec,

day = "20",

doi = "10.1002/ejic.202300552",

language = "English",

volume = "26",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "John Wiley & Sons Ltd",

number = "36",

}

TY - JOUR

T1 - Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**

AU - Liu, Jingjing

AU - Nodaraki, Lydia E.

AU - Martins, Daniel O. T. A.

AU - Giansiracusa, Marcus J.

AU - Cobb, Philip J.

AU - Emerson-King, Jack

AU - Ortu, Fabrizio

AU - Whitehead, George F. S.

AU - Gransbury, Gemma K.

AU - McInnes, Eric J. L.

AU - Tuna, Floriana

AU - Mills, David P.

PY - 2023/12/20

Y1 - 2023/12/20

N2 - We report the synthesis of a series of temperature-sensitive non-classical early Ln(II) (Ln = lanthanide) complexes, [K(2.2.2-cryptand)][Ln(Cptt)3] (Cptt = C5H3tBu2-1,3; 1-Ln; Ln = La-Nd). Complexes 1-Ln were typically prepared using Schlenk line techniques rather than more common glove box protocols, by the reduction of the parent Ln(III) complexes [Ln(Cptt)3] (2-Ln) with KC8 in THF in the presence of 2.2.2-cryptand at –30 °C. The majority of the 2-Ln series have been reported previously by the salt metathesis reactions of 3 eq. KCptt with parent LnCl3, and these methods were adapted here to afford 2-Pr. Complexes 1-Ln and 2-Pr were characterized by single crystal XRD, elemental analysis, ATR-IR and UV-Vis-NIR spectroscopy; 1-La and 2-Pr were additionally characterized by c.w. EPR spectroscopy, and variable temperature magnetic susceptibility measurements were performed on 2-Pr. During attempts to synthesize 2-Nd and 2-Sm we also obtained small crops of crystals of [Nd(Cptt)2(μ-I)]2 (3) and [Sm(Cptt)2(μ Cl)]2·C7H8 (4·C7H8), respectively; these complexes were also structurally authenticated. The combination of data obtained indicate that the Ln(II) centers in 1-Ln adopt 4fn5d1electron configurations, in common with other literature examples of [Ln(CpR)3]–anions (CpR = substituted cyclopentadienyl) for these metals.

AB - We report the synthesis of a series of temperature-sensitive non-classical early Ln(II) (Ln = lanthanide) complexes, [K(2.2.2-cryptand)][Ln(Cptt)3] (Cptt = C5H3tBu2-1,3; 1-Ln; Ln = La-Nd). Complexes 1-Ln were typically prepared using Schlenk line techniques rather than more common glove box protocols, by the reduction of the parent Ln(III) complexes [Ln(Cptt)3] (2-Ln) with KC8 in THF in the presence of 2.2.2-cryptand at –30 °C. The majority of the 2-Ln series have been reported previously by the salt metathesis reactions of 3 eq. KCptt with parent LnCl3, and these methods were adapted here to afford 2-Pr. Complexes 1-Ln and 2-Pr were characterized by single crystal XRD, elemental analysis, ATR-IR and UV-Vis-NIR spectroscopy; 1-La and 2-Pr were additionally characterized by c.w. EPR spectroscopy, and variable temperature magnetic susceptibility measurements were performed on 2-Pr. During attempts to synthesize 2-Nd and 2-Sm we also obtained small crops of crystals of [Nd(Cptt)2(μ-I)]2 (3) and [Sm(Cptt)2(μ Cl)]2·C7H8 (4·C7H8), respectively; these complexes were also structurally authenticated. The combination of data obtained indicate that the Ln(II) centers in 1-Ln adopt 4fn5d1electron configurations, in common with other literature examples of [Ln(CpR)3]–anions (CpR = substituted cyclopentadienyl) for these metals.

KW - cyclopentadienyl ligands

KW - EPR spectroscopy

KW - lanthanides

KW - low oxidation state

KW - synthetic methods

UR - http://www.scopus.com/inward/record.url?scp=85174592852&partnerID=8YFLogxK

U2 - 10.1002/ejic.202300552

DO - 10.1002/ejic.202300552

M3 - Article

AN - SCOPUS:85174592852

SN - 1434-1948

VL - 26

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 36

M1 - e202300552

ER -

Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

EPSRC National Research Facility for Electron Paramagnetic Resonance

Cite this

Non-Classical Early Lanthanide(II) Tris(di-tert-butylcyclopentadienyl) Complexes**

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Equipment

EPSRC National Research Facility for Electron Paramagnetic Resonance

Cite this