Polynuclear Lanthanide Complexes: Formation of a Selenium‐Centered Sm6 Complex, [{(C5Me5)Sm}6Se11]

Evans, William J.; Rabe, Gerd W.; Ansari, Mohammad A.; Ziller, Joseph W.

doi:10.1002/anie.199421101

Cited by 56 publications

(35 citation statements)

References 27 publications

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“…Sm2 is also the only metal center featuring μ 3 - and μ 5 -bridging iodo ligands exclusively. However, the Sm–C(Cp*) distances for Sm1–5 are all comparable to each other within the error limits (2.58(2)–2.70(2) Å; Table ) while similar to those in, for example, {[Cp*Sm] 6 Se 11 } . Surprisingly, it is the basal Sm5 atom that shows significantly longer Sm–I distances (Table ) and therewith should be assigned to the divalent state.…”

Section: Resultssupporting

confidence: 56%

“…However, the Sm−C(Cp*) distances for Sm1−5 are all comparable to each other within the error limits (2.58(2)−2.70(2) Å; Table 1) while similar to those in, for example, {[Cp*Sm] 6 Se 11 }. 61 Surprisingly, it is the basal Sm5 atom that shows significantly longer Sm−I distances (Table 1) and therewith should be assigned to the divalent state. The Sm(III)−μ 2 -I distances observed for complexes 2−4 (Table 1) are significantly shorter than those in divalent complex [Cp*Sm(μ 2 -I)(THF) 2 ] 2 (3.356(2)−3.459(2) Å).…”

Section: T H Imentioning

confidence: 96%

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

et al. 2016

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In this study, we demonstrate the structural variety of the Cp*SmI y system with respect to the amount of donor molecules (THF) present. The reaction of SmI2(THF)2 with 0.5 equiv of bis(pentamethylcyclopentadienyl)lead(II), PbCp*2, in THF gives the highly solvated monomeric complex Cp*SmI2(THF)3, when crystallized from THF. The same reaction performed in n-hexane followed by crystallization from toluene gave the partially solvated trimetallic complex [Cp*3Sm3I(μ2-I)3(μ3-I)2(THF)2]. Recrystallization of the Sm3 cluster from either C6D6 at ambient temperature or toluene at −40 °C produced the tetrametallic complex [Cp*4Sm4I(μ2-I)4(μ3-I)2(μ4-I)(THF)]. Reaction of SmI2, obtained via treatment of SmI2(THF)2 with excess AlEt3 in n-pentane, with 0.5 equiv of PbCp*2 in toluene led to the donor-free mixed-valent pentametallic complex [Cp*5Sm5(μ2-I)4(μ3-I)4(μ5-I)]. All compounds were characterized by single-crystal X-ray structure analysis.

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Section: Resultssupporting

confidence: 56%

Section: T H Imentioning

confidence: 96%

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

et al. 2016

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“…The Te–Te bond distances in such tellurides show elongation of about 13% with respect to the sum of the covalent radii and are typical for 3c-4e bonds [359]. A symmetric (Se 3 ) 4− ion was identified for the first time in the samarium/selenide cluster [{(C 5 Me 5 )Sm} 6 Se 11 ] [334], and considered a species isoelectronic to I 3 − . The Se–Se bond length in this system (2.749 Å) is much longer than the mean bond length in (Se 2 ) 2− species (2.37 Å).…”

Section: Trichalcogen(ide)smentioning

confidence: 99%

The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Aragoni¹,

Arca²,

Devillanova³

et al. 2007

Bioinorganic Chemistry and Applications

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The 3 centre-4 electrons (3c-4e) and the donor/acceptor or charge-transfer models for the description of the chemical bond in linear three-body systems, such as I3 − and related electron-rich (22 shell electrons) systems, are comparatively discussed on the grounds of structural data from a search of the Cambridge Structural Database (CSD). Both models account for a total bond order of 1 in these systems, and while the former fits better symmetric systems, the latter describes better strongly asymmetric situations. The 3c-4e MO scheme shows that any linear system formed by three aligned closed-shell species (24 shell electrons overall) has reason to exist provided that two electrons are removed from it to afford a 22 shell electrons three-body system: all combinations of three closed-shell halides and/or chalcogenides are considered here. A survey of the literature shows that most of these three-body systems exist. With some exceptions, their structural features vary continuously from the symmetric situation showing two equal bonds to very asymmetric situations in which one bond approaches to the value corresponding to a single bond and the second one to the sum of the van der Waals radii of the involved atoms. This indicates that the potential energy surface of these three-body systems is fairly flat, and that the chemical surrounding of the chalcogen/halogen atoms can play an important role in freezing different structural situations; this is well documented for the I3 − anion. The existence of correlations between the two bond distances and more importantly the linearity observed for all these systems, independently on the degree of their asymmetry, support the state of hypervalency of the central atom.

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“…[28] Not surprisingly, it is the ubiquitous cyclopentadienyl ligand system which triggered the formation of single-crystalline clusters, as revealed for mono(cyclopentadienyl) derivatives. [29][30][31][32][33] Until now, the size of such half-sandwich-based clusters is restricted to Ln 12 entities (dodecanuclear structures) of the general composition [Cp R LnX 2 ] 12 (Cp R =C 5 H 5 , Ln=Sm, X=Cl; Cp R =C 5 H 4 SiMe 3 , Ln=La, X=I, Br). [34,35] Herein, we report an extension of the previously discovered halogenation protocol applying half-sandwich lanthanide bis(tetramethylaluminato) complexes [Cp'Ln(AlMe 4 ) 2 ] (Cp'=C 5 H 4 SiMe 3 ) as cluster precursors.…”

Section: Introductionmentioning

confidence: 99%

Half‐Sandwich Complexes [Cp′₄Ln₄I₈]₄ (Ln=Ce, Pr):Emergence of Donor‐Free Organolanthanide Nanowheels

et al. 2021

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Dedicated to Professor Rinaldo Poli on the occasion of his 65th birthday. Slow diffusion of Me3 SiI into an n-hexane solution of lanthanide half-sandwich complexes [Cp'Ln(AlMe 4 ) 2 ] (Ln=Ce, Pr; Cp'=C 5 H 4 SiMe 3 ) gives access to the hexadecalanthanide ringcluster hybrids [Cp' 4 Ln 4 I 8 ] 4 , along with the cyclopentadienylbridged {Ce 8 } cluster [Cp' 4 Ce 4 I 7 (μ 2 -Cp)] 2 . On the contrary, direct addition of the halogenating reagent to complex [Cp'Ce-(AlMe 4 ) 2 ] in solution affords the spherical dodecanuclear cluster [Cp'CeI 2 ] 12 in addition to [Cp' 4 Ln 4 I 8 ] 4 . The isostructural bromide and chloride clusters [Cp'LnX 2 ] 12 (X=Cl, Br) were isolated via the same solution synthesis protocol, using the mild halogenido transfer reagents Me 3 GeX (X=Cl, Br). The reaction [Cp'Ce-(AlMe 4 ) 2 ]/Me 3 GeCl yielded the decanuclear heteroaluminato derivative [Cp' 5 Ce 5 Cl 9 (AlCl 2 Me 2 )] 2 as a coproduct. Attempts to isolate any intermediate species by performing the reaction at low temperature resulted in incomplete AlMe 4 /iodido exchange, affording the hexanuclear homoaluminate cluster [Cp' 6 Pr 6 I 8 (AlMe 4 ) 4 ]. All cerium clusters show bright photoluminescence under UV light. The luminescence properties of the dodecanuclear clusters [Cp'CeX 2 ] 12 (X=Cl, Br, I) were closer investigated.

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Polynuclear Lanthanide Complexes: Formation of a Selenium‐Centered Sm₆ Complex, [{(C₅Me₅)Sm}₆Se₁₁]

Cited by 56 publications

References 27 publications

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

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

The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Half‐Sandwich Complexes [Cp′₄Ln₄I₈]₄ (Ln=Ce, Pr):Emergence of Donor‐Free Organolanthanide Nanowheels

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Polynuclear Lanthanide Complexes: Formation of a Selenium‐Centered Sm6 Complex, [{(C5Me5)Sm}6Se11]

Cited by 56 publications

References 27 publications

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

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

The Nature of the Chemical Bond in Linear Three-Body Systems: From I3–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Half‐Sandwich Complexes [Cp′4Ln4I8]4 (Ln=Ce, Pr):Emergence of Donor‐Free Organolanthanide Nanowheels

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Polynuclear Lanthanide Complexes: Formation of a Selenium‐Centered Sm₆ Complex, [{(C₅Me₅)Sm}₆Se₁₁]

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

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

The Nature of the Chemical Bond in Linear Three-Body Systems: From I₃^–to Mixed Chalcogen/Halogen and Trichalcogen Moieties

Half‐Sandwich Complexes [Cp′₄Ln₄I₈]₄ (Ln=Ce, Pr):Emergence of Donor‐Free Organolanthanide Nanowheels