Heterometallic cuboidal clusters M3M′Q4 (M = Mo, W; M′= Sn, Pb, As, Sb; Q = S, Se):: From coordination compounds to supramolecular adducts

被引:18
作者
Hernandez-Molina, Rita [1 ]
Kalinina, Irina V. [2 ]
Abramov, Pavel A. [2 ]
Sokolov, Maxim N. [2 ]
Virovets, Alexandir V. [2 ]
Platas, Javier G. [3 ]
Llusar, Rosa [3 ]
Polo, Victor [3 ]
Vicent, Cristian [3 ]
Fedin, Vladimir P. [2 ]
机构
[1] Univ La Laguna, Dept Quim Inorgan, Tenerife, Islas Canarias, Spain
[2] Nikolaev Inst Inorgan Chem, Novosibirsk, Russia
[3] Univ Jaume 1, Dept Quim Fis & Analit, E-12071 Castellon de La Plana, Spain
关键词
D O I
10.1021/ic701581u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reactions of the incomplete cuboidal clusters [M(3)Q(4)(acaC)(3)(PY)(3)](+) (M = Mo, W; Q = S, Se) with group 14 and 15 metal complexes with the S(2)p(0) electronic configuration (AsPh3, SbPh3, SbCl3, Sbl(3), Pbl(3)(-), SnCl3-) led to heterometal incorporation with the formation of cuboidal clusters of the type [M-3(EX3)Q(4)(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 [M(3)Q(4)(acac)(3)(PY)(3)](+) (mu(2)-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 approximate to Sb; SbPh3 < Sbl(3) approximate to SbCl3; W3S4 < W3Se4. Interaction energies at the gas phase between [W(3)Q(4)(acac)(3)(py)(3)](+) (Q = S, Se) and SbX3 (X = 1, 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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页码:306 / 314
页数:9
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