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Synthesis of rare-earth-metal-in-cryptand dications, [Ln(2.2.2-cryptand)]2+, from Sm2+, Eu2+, and Yb2+ silyl metallocenes (C5H4SiMe3)2Ln(THF)2.

Daniel N. Huh, +5 more
- 01 Aug 2017 - 
- Vol. 53, Iss: 62, pp 8664-8666
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TLDR
A bimetallic, mixed-ligand metallocene/opened-crypt complex of Sm2+, [Sm(C16H32N2O6-κ2O:κ2 O')SmCp,''2], was obtained by KC8 reduction of Cp''2Sm(THF) [Cp'' = C5H3(SiMe3)2] in the presence of crypt.
About: 
This article is published in Chemical Communications.The article was published on 2017-08-01 and is currently open access. It has received 21 citations till now. The article focuses on the topics: Cryptand & 2.2.2-Cryptand.

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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2017

Frank T. Edelmann
- 01 Sep 2018 - 
TL;DR: In 2017, a significant increase in publications in the fields of organolanthanide and actinide chemistry over 2016 (195 vs. 155 publications) was reported in the journal Organometallics dedicated a special issue to the topic ‘Organometallic Actinide and Lanthanide Chemistry as mentioned in this paper.
Journal ArticleDOI

Tetramethylcyclopentadienyl Ligands Allow Isolation of Ln(II) Ions across the Lanthanide Series in [K(2.2.2-cryptand)][(C5Me4H)3Ln] Complexes

Tener F. Jenkins, +5 more
- 18 Oct 2018 - 
TL;DR: In this paper, a tetramethylcyclopentadienyl ligand was used to stabilize Ln(II) ions across the lanthanide series, which can also exist surrounded by three tetramerially-decompositioned cyclopentadiyl ligands.
Journal ArticleDOI

Photophysical characterization of a highly luminescent divalent-europium-containing azacryptate

Tyler C. Jenks, +7 more
- 01 May 2018 - 
TL;DR: A new luminescent EuII-containing complex is reported, leading to emission centered at 447 nm with a lifetime of 1.25 μs, and computational studies suggest that the steric bulk of the ligand is a major factor influencing the wavelength of emission.
Journal ArticleDOI

Spectroscopic and Electrochemical Trends in Divalent Lanthanides through Modulation of Coordination Environment

Tyler C. Jenks, +4 more
- 30 Jan 2020 - 
TL;DR: The influence of the ligand environment on complexes of YbII were studied and compared with analogous complexes of EuII, revealing the translatability of coordination environment effects across the divalent lanthanide series.
Journal ArticleDOI

Synthesis and reactivity of rare-earth metal phosphaethynolates.

Sebastian Bestgen, +3 more
- 25 Sep 2018 - 
TL;DR: These investigations comprise both +2 and +3 redox states, and one defined amidinate-based ligand set, as well as novel reaction pathways in the presence of the sequestering agents 18-crown-6 and 2,2,2-crypt.
References
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Journal ArticleDOI

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides

R. D. Shannon
- 01 Sep 1976 - 
TL;DR: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations as mentioned in this paper.
Journal ArticleDOI

Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr2+, Gd2+, Tb2+, and Lu2+

Matthew R. MacDonald, +4 more
- 22 May 2013 - 
TL;DR: These data, as well as density functional theory calculations and EPR spectra, suggest that a 4f(n)5d(1) description of the electron configuration in these Ln(2+) ions is more appropriate than 4f (n+1).
Journal ArticleDOI

f ? d transition energies of divalent lanthanides in inorganic compounds

Pieter Dorenbos
- 29 Jan 2003 - 
TL;DR: In this article, the authors derived the energy of divalent lanthanides from excitation and optical absorption spectra gathered from the literature and showed that the transition energy of one lanthanide in a compound can be predicted for all others in that same compound.
Journal ArticleDOI

Lanthanum does form stable molecular compounds in the +2 oxidation state.

Peter B. Hitchcock, +3 more
- 08 Feb 2008 - 
TL;DR: The reduction of the LaIII tricyclopentadienide complex by K and [18]crown-6 or [2,2-2]cryptand produced thermally stable mononuclear crystalline lanthanate(II) salts.
Journal ArticleDOI

Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C5H4SiMe3)3U]

Matthew R. MacDonald, +5 more
- 28 Aug 2013 - 
TL;DR: Density functional theory calculations indicate a 5f(3)6d(1) quintet ground state for the [Cp'3U](-) anion and match the observed strong transitions in its optical spectrum.
Related Papers (5)

Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln2+ Ions in the [K(2.2.2-cryptand)][(C5H4SiMe3)3Ln] Complexes: The Variable Nature of Dy2+ and Nd2+

Megan E. Fieser, +6 more
- 14 Jan 2015 - 

Oxidatively stable, aqueous europium(II) complexes through steric and electronic manipulation of cryptand coordination chemistry.

Nipuni Dhanesha H Gamage, +3 more
- 15 Nov 2010 - 

Synthesis of a crystalline molecular complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y].

Matthew R. MacDonald, +2 more
- 16 Sep 2011 - 

Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr2+, Gd2+, Tb2+, and Lu2+

Matthew R. MacDonald, +4 more
- 22 May 2013 - 

Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II)

Matthew R. MacDonald, +5 more
- 14 May 2012 - 
Frequently Asked Questions (6)
Q1. What is the oxidation state of a lanthanide?

Recent studies of reductive rare-earth metal chemistry have shown that the +2 oxidation state is available for all of the rare-earth metals (except Pm, which was not studied due to its radioactivity) as soluble molecular complexes, [K(crypt)][Cp03Ln] (Cp0 = C5H4SiMe3). 

A bimetallic, mixed-ligand metallocene/openedcrypt complex of Sm2+, [Sm(C16H32N2O6-j 2O:j2O0)SmCp0 02], was obtained by KC8 reduction of Cp0 02Sm(THF) [Cp0 0 = C5H3(SiMe3)2]in the presence of crypt. 

10 In addition, Ln(C6H3tBu3-1,3,5)2 complexes have been isolated for Ln = Nd, Tb, Dy, Ho, Er, and Lu that have the formal oxidation state of zero.11 Sm1+ is an attractive target since it could have a half-filled shell 4f7 electron configuration. 

1–6(1)A natural extension of the discovery of new +2 oxidation states is the pursuit of molecular complexes of lanthanide metals ions in the +1 oxidation state. 

only Eu, Yb, Sm, Tm, Dy, and Nd were thought to be capable of forming isolable +2 complexes based on the calculated redox potentials for the reduction of 4fn Ln3+ ions to 4fn+1 Ln2+ species.5,6 

The coordination geometry of the encapsulated Yb2+ is also irregular, but it can be approximated by a bicapped distorted octahedron with the nitrogen atoms in capping vertices.