Heterometallic Cuboidal Clusters M3M‘Q4 (M = Mo, W; M‘= Sn, Pb, As, Sb; Q = S, Se): From Coordination Compounds to Supramolecular Adducts
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Altres documents de l'autoria: Hernández Molina, Rita; Kalinina, Irina V.; Abramov, Pavel A.; Sokolov, Maxim; Virovets, Alexander V.; González Platas, Javier; Llusar, Rosa; Polo Ortiz, Victoriano; Vicent Barrera, Cristian; Fedin, Vladimir P.
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http://dx.doi.org/10.1021/ic701581u |
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Heterometallic Cuboidal Clusters M3M‘Q4 (M = Mo, W; M‘= Sn, Pb, As, Sb; Q = S, Se): From Coordination Compounds to Supramolecular AdductsAutoria
Data de publicació
2008Editor
American Chemical SocietyISSN
0020-1669Cita bibliogràfica
Inorganic Chemistry, 47, 1, p. 306-314Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
http://pubs.acs.org/doi/abs/10.1021/ic701581uVersió
info:eu-repo/semantics/publishedVersionResum
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 ... [+]
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]+ (μ2-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 ≈ Sb; SbPh3 < SbI3 ≈ 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. [-]
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