[NdI2(thf)5], the First Crystallographically Authenticated Neodymium(II) Complex

Bochkarev, M. N.; Fedushkin, Igor L.; Dechert, Sebastian; Fagin, A. A.; Schumann, Herbert

doi:10.1002/1521-3773(20010903)40:17<3176::aid-anie3176>3.0.co;2-y

Cited by 123 publications

(83 citation statements)

References 24 publications

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“…106 However, chemists never stopped pushing synthetic limits and, recently, low valent lanthanide chemistry has emerged as a fast developing field. [107][108][109] Recent advancements feature the synthesis and characterization of divalent lanthanide complexes for the complete lanthanide series, [110][111][112][113][114][115][116] reduced dinitrogen complexes, [117][118][119][120][121] reduced arene complexes, 26-29, 57, 122-126 and bimetallic reductive cleavage of aromatic C-H bonds. 40,44 Our group focused on the reduction chemistry of rare-earth metal complexes with non-innocent  ligands, followed by a small molecule activation study.…”

Section: Reduction Chemistry With  Ligands and Small Molecule Actmentioning

confidence: 99%

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Huang

Diaconescu

2016

Inorg. Chem.

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Our group has focused on the organometallic chemistry of rare-earth metals and actinides for a decade. By installing ferrocene diamide ligands at electropositive metal centers, we have been able to disclose unprecedented reactivity toward aromatic N-heterocycles, arenes, and other small molecules such as P 4 . Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and DFT calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor type interaction. Most noteworthy is that this interaction can be readily turned on or off by the addition or removal of a Lewis base. In addition to its flexible coordination, the redox active nature of the ferrocene backbone enabled us to explore redox-switchable transformations. The introduction of ferrocene-based ligands into organolanthanide chemistry not only helped to study intriguing fundamental problems but also led to fruitful chemistry including small molecule activation and controlled co-polymerization reactions.3

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Section: Reduction Chemistry With  Ligands and Small Molecule Actmentioning

confidence: 99%

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Huang

Diaconescu

2016

Inorg. Chem.

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“…[8] Second, the discovery that THF or DME would not be reduced by divalent thulium. [9] [TmI 2 (dme) 3 ] [10] followed by [DyI 2 (dme) 3 ] [11] and [NdI 2 -(thf) 5 ] [12] were the first molecular complexes of divalent thulium, dysprosium, and neodymium that could be handled in solution under argon (!) and crystallized.…”

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confidence: 99%

Superbulky Ligands and Trapped Electrons: New Perspectives in Divalent Lanthanide Chemistry

Meyer

2008

Angew Chem Int Ed

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electron localization · lanthanides · lanthanum · samarium · superbulky ligands have been known since the early decades of the 20th century. EuCl 2 , SmCl 2 , and YbCl 2 were the first to be reported. [1,2] For the elements europium, samarium, and ytterbium all twelve MX 2 halides are known. This is not the case for the elements thulium, dysprosium, and neodymium for which only the halides of the triad chlorine, bromine, and iodine have been synthesized and crystallographically characterized. They structurally bear close resemblance to the respective alkaline-earth metal halides. [3, 4] The electronic configurations of the M 2+ ions of these six elements are 6s 0 5d 0 4f n with n = 4 (Nd), 6 (Sm), 7 (Eu), 10 (Dy), 13 (Tm), and 14 (Yb).These halides are produced as solids either by comproportionation reactions (2 MX 3 + M) [4] or by Wöhlers metallothermic reduction from the trihalides with alkali metals.[4c]The reduction potentials for the reactions M 3+ + e À ! M 2+ range between À0.35 V (M = Eu) and À2.6 V (Nd), [5] the highest values being similar to that of the half cell K/K + (À2.92 V).[6] With the proper choice of ligand, it should be possible to produce these six lanthanides in solution in the oxidation state + 2 by alkali metal (potassium) reduction from trivalent precursors.There were two major discoveries in the outgoing 20th century that boosted the solution chemistry of divalent lanthanides: First, the synthesis of [Sm(C 5 Me 5 ) 2 ] [7] and the discovery that it reduces molecular nitrogen to form the dimeric [Sm 2 (C 5 Me 5 ) 4 N 2 ].[8] Second, the discovery that THF or DME would not be reduced by divalent thulium. [9] [TmI 2 (dme) 3 ][10] followed by [DyI 2 (dme) 3 ] [11] and [NdI 2 -(thf) 5 ] [12] were the first molecular complexes of divalent thulium, dysprosium, and neodymium that could be handled in solution under argon (!) and crystallized. Although these latter three complexes were not organometallic compounds, their existence has stimulated vigorous research with organic ligands and, meanwhile, there are organometallic examples for all of these six lanthanides in the oxidation state + 2. [13] Two strategies have proved successful: 1) The ligands should preferably be (super)bulky organic ligands. 2) The formation of an anionic complex in combination with a bulky cation enhances the stability by its gain in lattice energy. Two examples for the use of superbulky ligands alone were first reported in lectures at a conference on rare-earth metals ("Tage der Seltenen Erden 2007") in Bonn.

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“…SmI 2 ‐HMPA mixture: E red =−2.05 V vs. Ag/AgNO 3 in THF) . The three non‐classic lanthanide(II) iodides (LnI 2 ): thulium(II) iodide (TmI 2 , E red =−2.35 V vs. SCE in MeCN), dysprosium(II) iodide (DyI 2 , E red =−2.47 V vs. SCE in MeCN) and neodymium(II) iodide (NdI 2 , E red =−2.86 V vs. SCE in MeCN) have even stronger reducing power. For a catalytic use of lanthanide(II) iodides, stoichiometric amounts of metal (magnesium or zinc in combination with further additives, for example, silanes, or mischmetal) are added as co‐reductants .…”

Section: Methodsmentioning

confidence: 99%

Lanthanide Ions Coupled with Photoinduced Electron Transfer Generate Strong Reduction Potentials from Visible Light

Meyer

Slanina

Heckel

et al. 2017

Chemistry A European J

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Metal ions can have beneficial effects on photoinduced electron transfer. Merging such metal-ion-coupled electron transfer (MCET) with consecutive photoinduced electron transfer (conPET) enables the one-electron reduction of chlorobenzene with blue light in the presence of diisopropylethylamine as an electron donor. The presence of the metal ions extends the substrate scope of the photoredox catalysis to extreme reduction potentials (beyond -3 V vs. SCE).

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[NdI2(thf)5], the First Crystallographically Authenticated Neodymium(II) Complex

Cited by 123 publications

References 24 publications

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Superbulky Ligands and Trapped Electrons: New Perspectives in Divalent Lanthanide Chemistry

Lanthanide Ions Coupled with Photoinduced Electron Transfer Generate Strong Reduction Potentials from Visible Light

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