Die Kristallstruktur von SCl3[Re2Cl9] und ihre Verwandtschaft zum RuBr3-Typ

Rabe, Susanne; Müller, Ulrich

doi:10.1002/(sici)1521-3749(200004)626:4<830::aid-zaac830>3.0.co;2-a

Cited by 6 publications

(3 citation statements)

References 5 publications

(9 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previous calculations have shown that inclusion of relativistic effects in the optimization of metal−metal bond distances normally leads to poorer agreement with experimental data . A notable example is the [Re 2 Cl 9 ] - system, with an observed − Re−Re separation of 2.70−2.73 Å. The results of nonrelativistic calculations employing local functionals have been found to be in excellent agreement with the experimental data, but the incorporation of relativistic corrections has led to a considerable underestimation of the metal−metal bond length, by as much as 0.3 Å.…”

Section: Resultsmentioning

confidence: 95%

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems

Cavigliasso

Stranger

2003

Inorg. Chem.

View full text Add to dashboard Cite

Orbital overlap and spin polarization effects in Mo and W [M(2)X(9)](3)(-) halide and in [M(2)X'(3)X' '(6)](3)(-) mixed-halide systems have been investigated by means of density-functional calculations performed on the S = 0, S = 3, and reference states of these species. For the regular [M(2)X(9)](3)(-) systems, a strong linear correlation between the two factors has been obtained, and decreasing trends in both the overlap energy and the spin polarization energy upon descending the halide group have been observed. These trends can be related to the changes in the size and covalency of the ligands and in the nature of the metal-bridge interaction. For the mixed-ligand [M(2)X'(3)X' '(6)](3)(-) systems, important deviations (from the behavior of the regular systems), which are apparently the result of particular structural and energetic characteristics, have been observed.

show abstract

Section: Resultsmentioning

confidence: 95%

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems

Cavigliasso

Stranger

2003

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…The nonachlorodirhenate(IV) ion, which like V 2 Cl 3 (O(CH 3 ) 2 ) 6 + has a d 3 d 3 valence electron configuration, was first isolated in solution and in the solid state in the company of the tetrabutylammonium counterion . Subsequent characterization of the crystal structures of this compound, and of analogous compounds featuring bulky polychlorinated cations, − consistently reveals Re−Re distances in the range 2.70−2.725 Å.…”

Section: Resultsmentioning

confidence: 97%

DFT and Metal−Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

Petrie

Stranger

2004

Inorg. Chem.

View full text Add to dashboard Cite

Density functional theory (DFT) calculations are reported for 16 binuclear transition-metal complexes. Structural motifs studied include face-shared and edge-shared bioctahedra, carboxylate-bridged "paddlewheel" complexes, and nonbridged dimers possessing direct metal-metal bonds. Most of these structure types are represented both by multiply charged (tri- and tetra-anionic, and tetracationic) and by neutral or singly charged examples. Geometry optimizations for these species, in the vacuum phase, use the "broken-symmetry" approach coupled with nine different DFT methods. We find a clear dichotomy in the performance of different DFT approaches. For the eight neutral or singly charged complexes, orthodox gradient-corrected DFT methods such as BP and PBE perform generally very well in reproducing in vacuo the complex geometries obtained from X-ray crystallographic studies. In contrast, these orthodox approaches fail to reliably mimic the crystalline geometries for more highly charged complexes such as Mo(2)Cl(9)(3-), Cr(2)(CH(3))(8)(4-), and Rh(2)(NCCH(3))(10)(4+). Much closer agreement with experimental condensed-phase structures for the multiply charged dinuclear complexes is seen for two "local-density-approximation" approaches, X alpha and VWN, and for VWN+B-LYP, an unorthodox combination of the VWN local and B-LYP nonlocal density functionals. The very good performance of the latter approaches arises from an essentially fortuitous cancellation of errors: while the generally overbinding nature of these approaches suggests that they will not reliably describe true gas-phase structures, this overbinding compensates very well for the coulombic distortion expected when complexes are removed from the charge-stabilizing environment of the crystalline or solvated state. We recommend that, as an alternative to the (computationally expensive) incorporation of solvent-field corrections, VWN+B-LYP is the preferred method for structural characterization of triply or more highly charged dinuclear complexes, while orthodox approaches such as PBE perform best for neutral or mildly charged complexes.

show abstract

“…According to the authors' assumption, the first two compounds are polymers. The last compound, which has also been obtained by the interaction of metallic rhenium with sulfur dichloride at 400°C [8] [7], while with rhenium(VI) oxychloride [9], rhenium(VII) oxide [7] and rhenium(IV) chloride [8], a trinuclear cluster Re 3 S 7 Cl 7 of the structure [Re 3 (µ 3 -S)(µ-S 2 ) 3 Cl 6 ] + Clwas observed. In carbon disulfide, ReSCl 3 [5] is formed from the starting compound ReCl 5 in the presence of Sb 2 S 3 , and Re 2 S 4 Cl 7 [7] in the presence of S 2 Cl 2 , with subsequent transformation into the trinuclear complex Re 3 S 4 Cl 8 [7] at 250°C.…”

Section: Introductionmentioning

confidence: 99%

On the preparation, structure and bonding of ReSCl3

Волков¹,

Subbotin²,

Demchenko³

et al. 2015

Chem. Met. Alloys

View full text Add to dashboard Cite

The reaction of Re 2 O 7 with a solution of S in S 2 Cl 2 at 100°C produced rhenium sulfur trichloride, ReSCl 3. The compound was found to have a polymeric linear structure [{ReCl 2 (µ µ µ µ-Cl)} 2 (µ µ µ µ-S) 2 ] ∞ ∞ ∞ ∞ , which represents a new structure type (space group C2/m, a = 11.4950(7), b = 6.5626(3), c = 5.9938(4) Å, β = 95.199(4)°, Z = 4). The structure is closely related to the NbCl 4-type and expands the series of similar one-dimensional chain structures. Distorted Re[Cl 4 S 2 ] octahedra share edges to form infinite straight chains along the [010] direction and the Re atoms are arranged in pairs with alternatively short (2.965 Å) and long (3.598 Å) Re-Re distances. Electronic structure calculations and chemical bonding analysis, using the electron density/electron-localizability indicator (ELI) approach, indicated overall metallic character and revealed a combination of covalent polar Re-Cl and Re-S bonds and weak Re-Re non-polar metallic bonds, yielding the ELI-based oxidation numbers (ELIBON) Re +3.40 S-1.20 [Cl1-0.68 ] 2 Cl2-0.84 .

show abstract

Die Kristallstruktur von SCl3[Re2Cl9] und ihre Verwandtschaft zum RuBr3-Typ

Cited by 6 publications

References 5 publications

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems

DFT and Metal−Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

On the preparation, structure and bonding of ReSCl3

Contact Info

Product

Resources

About

Die Kristallstruktur von SCl3[Re2Cl9] und ihre Verwandtschaft zum RuBr3-Typ

Cited by 6 publications

References 5 publications

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M2X9]3- (M = Mo, W; X = F, Cl, Br, I) Systems

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M2X9]3- (M = Mo, W; X = F, Cl, Br, I) Systems

DFT and Metal−Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

On the preparation, structure and bonding of ReSCl3

Contact Info

Product

Resources

About

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems

Influence of the Ligand on the Coupling between the Metal-Based Electrons in Face-Shared [M₂X₉]³^- (M = Mo, W; X = F, Cl, Br, I) Systems