Synthesis, reactivity, and kinetics of substitution in W3PdSe4 cuboidal clusters. A reexamination of the kinetics of substitution of the related W3S4 cluster with thiocyanate.
Synthesis, reactivity, and kinetics of substitution in W3PdSe4 cuboidal clusters. A reexamination of the kinetics of substitution of the related W3S4 cluster with thiocyanate.
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DOI：
10.1021/ic802150x
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发表时间：
2009-04
影响因子：
4.6
通讯作者：
Andrés G. Algarra;M. Sokolov;J. González-Platas;M. J. Fernández-Trujillo;M. G. Basallote;R. Hernández-Molina-R.-Hernánde
中科院分区：
文献类型：
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作者：
Andrés G. Algarra;M. Sokolov;J. González-Platas;M. J. Fernández-Trujillo;M. G. Basallote;R. Hernández-Molina-R.-Hernánde
Pd(dba)(2) （dba =二苄基丙酮）与[W(3)Se(4)(H(2)O)(9)]（4+）在2 M HCl中反应得到立方体簇[W(3)(PdCl)Se(4)(H(2)O)(9)](3+)，并在Hpts溶液中发生边对边缩合结晶为边连接的双立方体簇[{W(3)PdSe(4)(H(2)O)(9)}(2)](pts)(8) × 18 H(2)O （pts(-) =对甲苯磺酸盐）。探讨了不同的配体，包括苯基亚磺酸盐PhSO(2)（-）取代Cl（-）。将苯基亚磺酸盐配合物与葫芦[6]uril (C(36)H(36)N(24)O(12)), [W(3)(Pd(PhSO(2))Se(4)(H(2)O)(8.58)Cl(0.42)](2)(C(36)H(36)N(24)O(12))Cl(5.16) x 16.83 H(2)O结晶为2:1加合物，并用x射线衍射测定了其结构。溶液研究表明，钯原子能够稳定亚磷酸和磷酸的锥体互变异构体：HP(OH)(2)和P(OH)(3)。对其与H(3)PO(2)和硫氰酸盐的反应进行了动力学研究，发现反应分别分为两个和三个动力学可分辨的步骤。根据文献中有关配合物的机理建议，对动力学结果进行了讨论。为了深入了解这类簇中取代动力学的细节，我们重新研究了相关的[W(3)S(4)(H(2)O)(9)]（4+）配合物与NCS（-）的反应，得到的结果首次提供了关于整套九配位水分子取代率的信息。
The reaction of Pd(dba)(2) (dba = dibenzylideneacetone) with [W(3)Se(4)(H(2)O)(9)](4+) in 2 M HCl gives the cuboidal cluster [W(3)(PdCl)Se(4)(H(2)O)(9)](3+), which undergoes edge-to-edge condensation and crystallizes from Hpts solutions as edge-linked double-cubane cluster [{W(3)PdSe(4)(H(2)O)(9)}(2)](pts)(8) x 18 H(2)O (pts(-) = p-toluenesulfonate). The substitution of Cl(-) by different ligands, including phenylsulfinate PhSO(2)(-), was explored. The phenylsulfinate complex was crystallized as a 2:1 adduct with cucurbit[6]uril (C(36)H(36)N(24)O(12)), [W(3)(Pd(PhSO(2))Se(4)(H(2)O)(8.58)Cl(0.42)](2)(C(36)H(36)N(24)O(12))Cl(5.16) x 16.83 H(2)O, and its structure was determined by X-ray diffraction. Solution studies indicate that the Pd atom is able to stabilize the pyramidal tautomer of hypophosphorous and phosphorous acid: HP(OH)(2) and P(OH)(3). Kinetic studies were carried out on the reactions with H(3)PO(2) and thiocyanate, which were found to proceed in two and three kinetically resolvable steps, respectively. The kinetic results are discussed in terms of the mechanistic proposals put forward in the literature for related complexes. To gain insight into the details of the substitution kinetics in these kinds of clusters, the reaction of the related [W(3)S(4)(H(2)O)(9)](4+) complex with NCS(-) has been reexamined, and the results obtained provide for the first time information about the rates of substitution of the whole set of nine-coordinated water molecules.