Prediction of Binary Lanthanide(III) Hydride Clusters LnnH3n (Ln = La, Gd, and Lu; n = 3 and 4)

Luo, Yi; Hou, Zhaomin

doi:10.1021/jp077318z

Cited by 22 publications

(14 citation statements)

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“…(l 2 -H)6 ] and [(H t Lu)3 (l 2 -H)6 ] clusters computed at the B3LYP/RSC-SDD(Ln)|6-3111G(p)(H) level are in excellent agreement with those computed by Luo and Hou,43 at the MP2/ RLC-SDD(Ln)|6-31111G(2p)(H) level. According to the WBO(LnÀ ÀLn) values the bonding in the Ln 3 ring of the [(H t Ln) 3 (l 2 -H) 6 ] q (Ln 5 La, Ce, Pr, Tm, Lu) clusters corresponds to very weak intermetallic orbital interactions, while in [(H t Yb) 3 (l 2 -H) 6 ] 32 the intermetallic YbÁÁÁYb interactions are marginal.…”

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confidence: 78%

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

et al. 2009

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Magnetoresponsive three-membered rings of d- and f-block elements have been thoroughly investigated with the help of electronic structure calculation methods. The magnetic response of the clusters was evaluated by the Nucleus Independent Chemical Shifts (NICS)(zz)-scan curves, which in conjunction with symmetry-based selection rules for the most significant translationally and rotationally allowed transitions helped rationalize and predict the orbital-type of aromaticity/antiaromaticity of the clusters. The magnetoresponsive early (Groups 3, 4, and 5) transition metal M(3) rings exhibit successive aromatic and antiaromatic zones separated by a nodal plane. The magnetoresponsive late (Groups 11 and 12) transition metal M(3) rings exhibit long-range aromatic zone with the NICS(zz)(R) values decaying rapidly and monotonically with respect to R. The magnetic response of Group 10 transition metal M(3) rings is similar to that of the early transition metal M(3) rings, but it is long-range antiaromatic only for the [c-Ni(3)] cluster. The NICS(zz)-scan curve of the [(H(t)La)(3)(mu(2)-H)(6)] cluster is indicative of weak pure sigma-aromaticity due to the induced diatropic ring current from the translationally allowed a(1)(') --> e' and e' --> a(1)(') transitions. The aromatic-antiaromatic behavior of the [(H(t)Ce)(3)(mu(2)-H)(6)](+) and [(H(t)Tm)(3)(mu(2)-H)(6)](2-) clusters is similar to that of the early d-block elements. The magnetic response of [(H(t)Yb)(3)(mu(2)-H)(6)](3-) is similar to that of [c-Hg(3)](2-). The [(H(t)Lu)(3)(mu(2)-H)(6)] cluster can be considered as a doubly (sigma + pi) aromatic system, with the sigma-aromatic component being much stronger than the pi-aromatic one. Finally, the [(X(t)Re)(3)(mu(2)-X)(6)] and [(X(t)Ru)(3)(mu(2)-X)(6)](+) (X = Cl, Br, I) clusters exhibit significant aromatic character with the greatest contribution to the induced diatropic ring currents coming from pi-type transitions.

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confidence: 78%

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

et al. 2009

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“…Unlike in [Y 4 (η 5 -C 5 Me 4 SiMe 3 ) 4 Organometallics XXXX, XXX, XXX−XXX reported previously. 10 This structure is less stable than I by 13.6 kcal·mol −1 . The Y···Y and Y−H distances are similar to those found for structure I ( Table S2 in the Supporting Information).…”

Section: ■ Introductionmentioning

confidence: 93%

Yttrium Dihydride Cation [YH₂(THF)₂]⁺_n: Aggregate Formation and Reaction with (NNNN)-Type Macrocycles

et al. 2015

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Monocationic bis(hydrocarbyl)yttrium complexes [YR 2 (THF) 2 ][A] (R = CH 2 SiMe 3 , CH 2 C 6 H 4 -o-NMe 2 ; A = weakly coordinating anion) underwent hydrogenolysis using dihydrogen or phenylsilane to give a mixture of polynuclear solvent-stabilized dihydride cations [YH 2 (THF) 2 ] n [A] n . The mixture composition as well as the nuclearity n depended on the starting material, solvent, and reaction conditions. NMR spectroscopic data in solution and X-ray diffraction data suggested that the main product was tetranuclear, although conclusive structural data were not obtained. DFT calculations supported a closo-type tetrahedral [YH 2 (THF) 2 ] 4 4+ core. The hydridic character of these cations was revealed by their reaction with benzophenone to give the bis (diphenylmethoxy) cation [Y(OCHPh 2 ) 2 (THF) 4 ][AlR 4 ]. The reaction of this cluster with the (NNNN)-type macrocycle Me 4 TACD under dihydrogen gave the dinuclear tetrahydride dication with quadruply bridging hydride ligands, [Y 2 (μ-H) 4 (Me 4 TACD) 2 ][A] 2 , analogous to the previously characterized lutetium derivative. NH-acidic (Me 3 TACD)H gave the dinuclear dihydride dication [Y 2 (μ-H) 2 (Me 3 TACD) 2 (THF) 2 ][A] 2 . ■ INTRODUCTIONIn contrast to interstitial rare-earth metal hydrides of the type LnH n (n = 2, 3), molecular hydrides of these large, electropositive, and Lewis acidic metals are commonly stabilized as bis-or mono(cyclopentadienyl) hydride complexes [Ln(η 5 -C 5 R 5 ) n H 3−n ] (n = 2, 1). 1 They are easily prepared by σ-bond metathesis of the corresponding hydrocarbyl compounds [Ln(η 5 -C 5 R 5 ) n R′ 3−n ] (n = 2, 1) with dihydrogen or phenylsilane. 1 Cationic hydrocarbyl complexes of the rare-earth metals [LnR 2 (THF) 2 ][A] are easily accessible by protonolysis of the parent neutral complexes with Brønsted acidic ammonium salts of weakly coordinating borate anions or with Lewis acidic boranes, tris(alkyl)aluminum, and trityl salts. 3 In the presence of weakly coordinating neutral donor ligands L, hydrogenolysis with dihydrogen or phenylsilane should lead to cationic dihydrides of the formula [LnH 2 (L) n ] + . We describe here details of the long quest for yttrium compounds of the type [YH 2 (L) n ] + , solely coordinated by neutral donor ligands such as tetrahydrofuran (THF), tetrahydropyran (THP), or crown ethers, 2 as well as the characterization of an (NNNN)-type macrocycle-stabilized dimer [Y 2 (μ-H) 4 (Me 4 TACD) 2 ] 2+ featuring a quadruple hydride bridge.

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“…Theoretical investigations on the binary hydrides [LnH 3 ] x (Ln = La and Gd) predict the possible existence of trinuclear and tetranuclear cores. [10] 2.1. Dihydrides of the Type [(L n X)LnH 2 ]…”

Section: Neutral Rare-earth-metal Hydridesmentioning

confidence: 99%

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

et al. 2014

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Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

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Prediction of Binary Lanthanide(III) Hydride Clusters Ln_nH₃_n (Ln = La, Gd, and Lu; n = 3 and 4)

Cited by 22 publications

References 23 publications

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

Yttrium Dihydride Cation [YH₂(THF)₂]⁺_n: Aggregate Formation and Reaction with (NNNN)-Type Macrocycles

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

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Prediction of Binary Lanthanide(III) Hydride Clusters LnnH3n (Ln = La, Gd, and Lu; n = 3 and 4)

Cited by 22 publications

References 23 publications

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

Diagnosis of magnetoresponsive aromatic and antiaromatic zones in three‐membered rings of d‐ and f‐block elements

Yttrium Dihydride Cation [YH2(THF)2]+n: Aggregate Formation and Reaction with (NNNN)-Type Macrocycles

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

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Prediction of Binary Lanthanide(III) Hydride Clusters Ln_nH₃_n (Ln = La, Gd, and Lu; n = 3 and 4)

Yttrium Dihydride Cation [YH₂(THF)₂]⁺_n: Aggregate Formation and Reaction with (NNNN)-Type Macrocycles