Homoleptic Rare‐Earth Carbazolates and the Trends of Their E Redox Potentials: Mixed‐Valent Samarium in ¹_∞[Sm₂(Cbz)₅](CbzH) (CbzH = carbazole) and Trivalent Thulium, Neodymium and Gadolinium in [Ln₂(Cbz)₆]

Abstract

The solvent-free melt reaction of carbazole (CbzH, C 12 (4), respectively. Compounds 1 and 2 were obtained as single crystals and their crystal structures determined by single-crystal X-ray analysis, whilst 3 and 4 were obtained as powders. X-ray powder diffraction studies show that the gadolinium-containing complex 4 is isotypic to the thulium complex 2, whereas the neodymium-containing complex 3 is not. Compound 1 contains alternating Sm II and Sm III cations in a chain structure. Complex 2 only exhibits dimeric units of Tm III . Besides Ln−N coordination, the crystal structures of

Europium bis(dimethylsilyl)amides including mixed-valent Eu3[N(SiHMe2)2]6[μ-N(SiHMe2)2]2

“…Three distinct conformers in the asymmetric unit are unique to this europium derivative. 28 The reaction of metallic ytterbium, (C 6 H 5 )Hg(C 6 30 Redox reaction of divalent [Yb(C 9 H 7 ) 2 (THF) 2 ] in either a 1 : 2 or 1 : 1 molar ratio with a diazabutadiene gives dinuclear [Yb 2 (µ-η 5 :η 4 -C 9 H 7 )(η 5 -C 9 H 7 ) 2 {µ-η 4 :η 4 -PhNC(Me)v C(Me)NPh}] or tetranuclear [Yb 2 (µ-η 5 :η 4 -C 9 H 7 )(η 5 -C 9 H 7 ) 2 {µ-η 4 :η 4 -PhNC(CH 2 )vC(Me)NPh}] 2 , respectively. The foremost conformational differences are due to rotation of the silyl groups around the Si-N bond.…”

Group 3 Elements and Lanthanide Metals

“…E 0 LnII/LnIII of -1.55 V for Sm and E 0 LnIII/LnIV = 1.7 V for Ce show the constraints of the related redox force of the respective ion to enter the trivalent state, which is mostly accompanied by decomposition of the linker. Despite Sm(II) and Ce(IV) complexes and few coordination polymers [23][24][25], no corresponding MOFs have been reported. As the redox potentials of the other lanthanides and especially of the group 3 metals are even more extreme, the chance to keep a ligand from decomposing while synthesizing a MOF is very limited.…”

3D-[Pr(Im)3(ImH)]@ImH: Ein dreidimensionales Netzwerk mit vollständiger Stickstoffkoordination aus einer Imidazolschmelze / 3D-[Pr(Im)3(ImH)]@ImH: A Three-Dimensional Network with Complete Nitrogen Coordination Obtained from an Imidazole Melt

“…Gerade für eine sauerstoff-und halogenfreie Koordinationschemie ist die gleichsam erreichbare Vermeidung von Coliganden attraktiv, da die Bildung vollständiger Stickstoff-Koordinationssphären aus Lö-sung sonst zumeist an multichelatisierende Liganden gebunden ist [12 -16]. Wie bereits für Pyrazolate [8,9,17], Carbazolate [6,7] oder Benzotriazolate [18] gezeigt, können N-Heterozyklen ferner dazu neigen, eindimensionale Koordinationspolymere zu bilden. Der Einsatz dergleichen Liganden in Lösung wie in Ln-Carbazolaten [19,20] oder mit * ImH = imidazole, C 3 H 3 N 2 H; Im − = imidazolate anion, C 3 H 3 N 2 − .…”