Heterometallic cuboidal clusters M(3)M'Q(4) (M = Mo, W; M'= Sn, Pb, As, Sb; Q = S, Se): from coordination compounds to supramolecular adducts
| Autor: | Javier G. Platas, Vladimir P. Fedin, Cristian Vicent, Rosa Llusar, Rita Hernández-Molina, Victor Polo, I. V. Kalinina, Pavel A. Abramov, A. V. Virovets, Maxim N. Sokolov |
|---|---|
| Rok vydání: | 2007 |
| Předmět: |
chemistry.chemical_classification
Chemistry Supramolecular chemistry Interaction energy Coordination complex Adduct Inorganic Chemistry Metal Crystallography chemistry.chemical_compound Octahedron visual_art visual_art.visual_art_medium Cluster (physics) Phenyl group Physical and Theoretical Chemistry |
| Zdroj: | Inorganic chemistry. 47(1) |
| ISSN: | 0020-1669 |
| Popis: | Reactions of the incomplete cuboidal clusters [M3Q4(acac)3(py)3]+ (M = Mo, W; Q = S, Se) with group 14 and 15 metal complexes with the s2p0 electronic configuration (AsPh3, SbPh3, SbCl3, SbI3, PbI3-, SnCl3-) led to heterometal incorporation with the formation of cuboidal clusters of the type [M3(EX3)Q4(acac)3(py)3]n+ (n = 0 for Sn, Pb; n = 1 for As, Sb), whose structures were determined by X-ray diffraction. The cuboidal clusters can be described as complexes of the cluster tridentate ligand [M3Q4(acac)3(py)3]+ (mu2-chalcogen atoms as donors) with the EX3, where the E atom attains a distorted octahedral coordination. Analysis based on the bond distances E-Q gives the following sequence of affinity: As < Sb; Pb < Sn approximately Sb; SbPh3 < SbI3 approximately SbCl3; W3S4 < W3Se4. Interaction energies at the gas phase between [W3Q4(acac)3(py)3]+ (Q = S, Se) and SbX3 (X = I, Ph) were computed at the DFT level (BP86/TZP). The magnitude of the interaction depends strongly on the substituents at Sb, and the replacement of iodine by the phenyl group decreases the interaction energy from -9.21 to -2.70 kcal/mol and from -12.73 to -3.85 kcal/mol for the W3SbS4 and W3SbSe4 cores, respectively. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|