Modeling η5‐C5Me4SiMe3 with η3‐C3H5 for DFT study of a tetranuclear yttrium polyhydrido complex [(η5‐C5Me4SiMe3)YH2]4

Luo, Yi; Hou, Zhaomin

doi:10.1002/qua.21169

Cited by 7 publications

(1 citation statement)

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“…As part of our research project on understanding of the synergistic effects of multimetallics, we previously reported computational studies of the structure and reactivity of a series of multinuclear rare-earth and transition-metal complexes, − including the activation of dinitrogen (N 2 ) by the titanium hydride cluster 1 . In this paper, we wish to report the DFT studies of the reaction of benzene with the trinuclear titanium hydride cluster 1 (Figure b) .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

Kang

Luo

et al. 2016

J. Am. Chem. Soc.

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Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

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Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

Kang

Luo

et al. 2016

J. Am. Chem. Soc.

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

Luo

Hou

2007

J. Phys. Chem. C

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Modeling η⁵‐C₅Me₄SiMe₃ with η³‐C₃H₅ for DFT study of a tetranuclear yttrium polyhydrido complex [(η⁵‐C₅Me₄SiMe₃)YH₂]₄

Cited by 7 publications

References 34 publications

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

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

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

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Modeling η5‐C5Me4SiMe3 with η3‐C3H5 for DFT study of a tetranuclear yttrium polyhydrido complex [(η5‐C5Me4SiMe3)YH2]4

Cited by 7 publications

References 34 publications

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

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

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

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Modeling η⁵‐C₅Me₄SiMe₃ with η³‐C₃H₅ for DFT study of a tetranuclear yttrium polyhydrido complex [(η⁵‐C₅Me₄SiMe₃)YH₂]₄

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

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