[(Cp*RuCl)2(μ-Cl)2]: Bond-Stretch or Spin-State Isomerism?

McGrady, John E.

doi:10.1002/1521-3773(20000901)39:17<3077::aid-anie3077>3.0.co;2-b

Cited by 38 publications

(8 citation statements)

References 22 publications

(18 reference statements)

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“…While the existence of true bond-stretch isomers is a rare occurrence, some of the better known examples involve polynuclear transition metal complexes, including the dinuclear system [(Cp*RuCl) 2 (μ-Cl) 2 ] , and trinuclear species of the type [M 3 (dpa)L 2 ] or [M 3 (dpa)LL′], where M = Co or Cr, dpa is the dipyridilamide anion, and L, L′ are either halogens or molecular anions. − A number of linear trinuclear [M 3 X 12 ] z − systems have also been reported including complexes with M = Ru, Mo, and Ti and X = Cl, Br, and I. ,,− These systems exhibit significant variation in their structural and magnetic properties and, consequently, the extent of metal–metal interaction. The mixed-valence [Ru 3 Cl 12 ] 4– system, which comprises a central Ru II and terminal Ru III ions, has been structurally characterized with a Ru–Ru distance of 2.805 Å .…”

Section: Introductioncontrasting

confidence: 99%

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes

2015

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Metal-metal bonding in structurally characterized In4Ti3Br12, comprising linear, mixed-valence d(1)d(2)d(1) face-shared [Ti3Br12](4-) units with a Ti-Ti separation of 3.087 Å and strong antiferromagnetic coupling (Θ = -1216 K), has been investigated using density functional theory. The antiferromagnetic configuration, in which the single d electron on each terminal Ti(III) (d(1)) metal center is aligned antiparallel to the two electrons occupying the central Ti(II) (d(2)) metal site, is shown to best agree with the reported structural and magnetic data and is consistent with an S = 0 ground state in which two of the four metal-based electrons are involved in a two-electron, three-center σ bond between the Ti atoms (formal Ti-Ti bond order of ∼0.5). However, the unpaired spin densities on the Ti sites indicate that while the metal-metal σ interaction is strong, the electrons are not fully paired off and consequently dominate the ground state antiferromagnetic coupling. The same overall partially delocalized bonding regime is predicted for the other three halide [Ti3X12](4-) (X = F, Cl, I) systems with the metal-metal bonding becoming weaker as the halide group is descended. The possibility of bond-stretch isomerism was also examined where one isomer has a symmetric structure with identical Ti-Ti bonds while the other is unsymmetric with one short and one long Ti-Ti bond. Although calculations indicate that the latter form is more stable, the barrier to interconversion between equivalent unsymmetric forms, where the short Ti-Ti bond is on one side of the trinuclear unit or the other, is relatively small such that at room temperature only the averaged (symmetric) structure is likely to be observed.

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Section: Introductioncontrasting

confidence: 99%

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes

2015

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“…Vosko-Willk-Nusair(VWN)H [38] H 参数化的局域密度近似 (LDA), 交换和相关泛函采用 BeckH [39] H 梯度校正和 PerdewH [40] H 非局域校正. 三zeta加极化函数(TZP)描述价层电子, 内层 (O, 1s; Mn, P, 1s-2p; As, Se, 1s-3p; Mo, 1s-3d)采取冻核近似, 相对论效应使用零阶正则 (ZORA)近似H [41] 的结构用来计算BS态的性质是一种合理的近似H [42] H. a) 括号中的数据来自于X-ray 晶体结构H [15] H…”

Section: 而讨论过渡金属取代多酸结构中磁中心unclassified

密度泛函研究双核MnII取代的杂多酸[MnII2(X<italic>n</italic>+Mo9O33)2]2(n-10)- (X = PV, As

方亮¹,

关威²,

颜力楷³

et al. 2009

SSB

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“…By removal of all symmetry elements connecting the two manganese centers, the full symmetry C 2h was lowered to C 2 . As expected, such systems undergo minor structural changes when a change of spin state occurs, so it is a reasonable approximation that the HS state optimized geometry is used to clarify the BS state properties for the studied systems [42] .…”

Section: Computational Detailsmentioning

confidence: 99%

Density functional study of magnetic exchange of dinuclear manganese complexes with the heteropolymolyanion: [MnII 2(X n+Mo9O33)2]2(n−10)− (X = PV, AsV, SeVI)

Fang

Guan

Yan

et al. 2008

Sci. China Ser. B-Chem.

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The magnetic exchange interactions between the dimanganese(II)-substituted complexes and the heteropolymolyanion, [Mn II2 (X n+ Mo 9 O 33 ) 2 ] 2(n-10)-(X = P V (I), As V (II) and Se VI (III)), are investigated by using density functional theory combined with broken-symmetry approach (DFT-BS) method. The calculated magnetic exchange coupling constant (J) of complex II is in reasonable agreement with the responding experimental value and the negative J values indicate that antiferromagnetic exchange interactions exist in these complexes. Furthermore, the influence of the central heteroatom on the exchange coupling within the dimanganese core unit is studied from standpoints of geometry, spin density and frontier orbitals. It demonstrates that the change of the heteroatom X via P V -As V -Se VI elongates the distances of Mn 1 ···Mn 2 and shortens the distances of O b ···O b , and reduces the effectiveness of the superexchange pathways, consequently, decreasing the magnitude of the antiferromagnetic coupling constant, J, of these species.

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[(Cp*RuCl)2(μ-Cl)2]: Bond-Stretch or Spin-State Isomerism?

Cited by 38 publications

References 22 publications

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes

密度泛函研究双核Mn<sup>II</sup>取代的杂多酸[Mn<sup>II</sup><sub>2</sub>(X<sup><italic>n</italic>+</sup>Mo<sub>9</sub>O<sub>33</sub>)<sub>2</sub>]<sub>2</sub><sup>(n-10)-</sup> (X = P<sup>V</sup>, As<sup>

Density functional study of magnetic exchange of dinuclear manganese complexes with the heteropolymolyanion: [MnII 2(X n+Mo9O33)2]2(n−10)− (X = PV, AsV, SeVI)

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[(Cp*RuCl)2(μ-Cl)2]: Bond-Stretch or Spin-State Isomerism?

Cited by 38 publications

References 22 publications

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti3X12]4– (X = F, Cl, Br, I) Face-Shared Complexes

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti3X12]4– (X = F, Cl, Br, I) Face-Shared Complexes

Density functional study of magnetic exchange of dinuclear manganese complexes with the heteropolymolyanion: [MnII 2(X n+Mo9O33)2]2(n−10)− (X = PV, AsV, SeVI)

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Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes

Metal–Metal Bonding in Trinuclear, Mixed-Valence [Ti₃X₁₂]^4– (X = F, Cl, Br, I) Face-Shared Complexes