Displacement, reduction, and ligand redistribution reactivity of the cationic mono-C5Me5 Ln2+ complexes (C5Me5)Ln(BPh4) (Ln=Sm, Yb)

Lewis‐Acid Stabilized Organoimide Complexes of Divalent Samarium, Europium, and Ytterbium

“…[12] The YbÀNd istances involving the m 2 -bridgingi mido moieties are 2.263(3) (1-Yb)a nd 2.302(2) (2-Yb a )( Ta ble1), which are significantly shorter when compared to the YbÀNc ontacts of 2.352(4) to 2.430 (5) 4 ,f eaturing m 3 -homobridging imido ligands. [26] For furtherc omparison, the YbÀN distances of four-coordinate Yb II [35] and the five-coordinate dimericy tterbium(II) amide [Cp*Yb{N(SiMe 3 ) 2 }] 2 , [36] (m 2 -bridging, 2.453(2) and 2.622 (2) )are considerably longer.…”

Donor-Solvent-Dependent Cluster Formation of (C5Me5)SmI2(THF)x-Type Half-Sandwich Complexes

“…Overall, the samarium atoms span the base of a trigonal bipyramid, with the two μ 3 -bridging iodo ligands representing the vertices of the pyramids and the three μ 2 -bridging iodo ligands engaging in an almost planar six-membered metallacycle. Such trimetallic units [Ln 3 (μ 2 -X) 3 (μ 3 -X) 2 ] are quite common in rare-earth-metal coordination chemistry, − and the most relevant examples comprise [Cp 3 Yb 3 (μ 3 -Cl) 2 (μ-Cl) 3 (THF) 3 ]­[Cp 6 Yb 6 (μ 6 -Cl)­(μ-Cl) 12 ], [Y 3 (O t Bu) 3 (X)­(μ 2 -O t Bu) 3 ­(μ 3 -O t Bu)­(μ 3 -Cl)­(THF) 2 ] (X = Cl, O t Bu), , [Er 3 (OAr OMe ) 4 (μ 2 -F) 3 ­(μ 3 -F) 2 (THF) 4 ], [L 3 Gd 3 Cl 5 ]­[B­(C 6 F 5 ) 4 ] (with L being a β-diketiminato ligand), and the very similar samarium complex [{Cp*Sm­(THF)} 3 ­(μ-Cl) 5 ]­[BPh 4 ], which was obtained by an oxidation reaction involving Cp*Sm­[BPh 4 ] and tert -butyl chloride (Scheme ).…”

“…10 Instead the trimeric THF-depleted complex [Cp* 3 Sm 3 I(μ 2 -I) 3 (μ 3 -I) 2 (THF) 2 ] (2), with only 2/3 molar equiv of THF left, could be identified by X-ray crystallography (Figure 3, Table 1, Table S1). 43 (with L being a β-diketiminato ligand), and the very similar samarium complex [{Cp*Sm- 15 which was obtained by an oxidation reaction involving Cp*Sm[BPh 4 ] and tert-butyl chloride (Scheme 1).…”

“…Most of these examples were investigated by the Evans group dealing mainly with organosamarium­(II) precursors (Scheme ). − The type of ancillary ligand affects markedly the reaction outcome in terms of ligand redistribution (metallocene versus half-sandwich versus homoleptic complex). For example, the halogenated species Cp* 2 SmX­(THF) (X = Cl, I) were elegantly obtained from Cp* 2 Sm­(THF) 2 and 1,2-diiodoethane and tert -butyl chloride, respectively …”

Radical Cleavage of Al–C Bonds Promoted by Phenazine: From Noninnocent Ligand to Radical Abstractor

“…Phenazine is particularly versatile, since it may act as both a regular neutral donor and a reduced ligand, engaging in electron transfer reactions with a wide variety of elements, including lanthanides and actinides . However, the reactivity with alane, as reported by Heunish in 1972 on the basis of EPR evidence, seems to suggest the formation of stable radical species .…”