octacyanotungstate(IV)(4-)

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: octacyanotungstate(IV)(4-)
• 英文别名: octacyanotungstate(IV)
• 化学式: C₈N₈W
• 分子量: 391.992
• InChiKey: DXWKDNILKAJQNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.13
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  190.32
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  octacyanotungstate(IV)(4-) 、 (SCN)2 radical anion 以 水 为溶剂， 生成 硫氰酸酯
  参考文献：
  名称：

  二卤化物和叠氮化物自由基与无机还原剂反应的速率常数的温度依赖性

  摘要：

  Rate constants for several reactions of inorganic radicals with inorganic reductants in aqueous solutions have been measured by pulse radiolysis as a function of temperature, generally between 5 and 75-degrees-C. The reactions studied were of the dihalide radicals, Cl2.-, Br2.-, and I2.-, the (SCN)2.- radical, and the neutral radical N3., reacting with the substitution-inert metal complexes, Fe(CN)6(4-), Mo(CN)8(4-), and W(CN)8(4-), and with the anions SO3(2-), HSO3-, NO2-, and ClO2-. The rate constants measured were in the range of 10(6) to 5 x 10(9) M-1 s-1 and the calculated Arrhenius activation energies ranged from 5 to 35 kJ mol-1. The preexponential factors also varied considerably, with log A ranging from 8.9 to 13.1. The temperature dependence of the reaction rate constant is correlated to the reaction exothermicity for the metal complexes, which apparently react by outer-sphere electron transfer. The simple anions, however, have lower activation energies, which do not correlate well with the exothermicities, suggesting that these anions probably react by an inner-sphere mechanism.

  DOI：

  10.1021/j100161a050
• 作为产物：
  描述：

  octacyanotungstate(V) (3-) 在 羟胺 作用下， 生成 octacyanotungstate(IV)(4-)
  参考文献：
  名称：

  分光光度法测定酸性和碱性介质中羟胺还原八氰基非钨酸盐（V）的反应化学计量

  摘要：

  通过分光光度法研究了碱性和酸性介质中羟胺还原八碳烯基非钨酸盐（V）的化学计量。已经发现，W（CN）8 3-和羟胺之间的化学计量比在碱性介质中为2：1，在酸性介质中为1：1，与先前提出的值一致。

  DOI：

  10.1016/s0277-5387(00)80359-9

文献信息

• Kinetics and salt effects of the reduction of octacyanomolybdate(V) and octacyanotungstate(V) by sulphite ions
  作者：Charles R. Dennis、Stephen S. Basson、Johann G. Leipoldt

  DOI：10.1016/s0277-5387(00)84399-5

  日期：1983.1

  The kinetics of the reduction of octacyanomolybdate(V) and octacyanotungstate(V) by sulphite ions has been studied over a wide pH range. The reaction is catalysed by alkali metal ions. The rate law is found to be of the form: The third order rate constants at [OH−] = 0.05 mol dm−3 for the reduction of Mo(CN)83− and W(CN)3−8 were determined as 6.2 x 103dm6mol−2 s−1 and 22.3 dm6mol−2s−1 respectively

  在较宽的pH范围内，已研究了亚硫酸根离子还原八氰基钼酸盐（V）和八氰基钨酸盐（V）的动力学。该反应由碱金属离子催化。率法被发现是以下形式：在第三速率常数[OH - ] = 0.05摩尔分米-3对的Mo（CN）的还原8 3-和W（CN）3- 8测定为6.2 x + 10 3 dm 6 mol -2 s -1和22.3 dm 6 mol -2 s -1在A + = Na +且K a时在298 K亚硫酸氢根离子的离子强度被确定为2.4×10 -8 mol dm -3。已经确定反应是通过外球机理进行的。提出了对碱金属离子催化的解释。
• [PPh₄]₃[W(CN)₇(O₂)]·4H₂O as the Representative of the [M(L)₇(LL)] Class for Nine-Coordinate Complexes
  作者：Dariusz Matoga、Janusz Szklarzewicz、Masahiro Mikuriya

  DOI：10.1021/ic060523t

  日期：2006.9.1

  a paucity of structurally characterized cyano-peroxo complexes of Mo and W. The side-on coordination mode of the peroxo moiety in [W(CN)7(eta2-O2)]3- has been ascertained with X-ray crystal structure determination [d(O-O) = 1.41 A; peroxo bite angle: 41.0 degrees ] and corroborated with vibrational spectroscopy [nu(O-O) = 915 cm(-1)]. The complex ion exhibits trapezoidal tridecahedral geometry and represents

  在环境条件下，水溶液中[W（CN）8] 4-中W-CN键的光诱导解离，以及分子氧的吸收，提供了W（VI）混合配体络合物阴离子[W（ CN）（7）（eta2-O2）] 3-，可方便地分离为其[PPh4 +]盐。尽管几十年来一直对氰钼酸盐和氰钨酸盐的化学研究进行了极大的兴趣和勃勃生机，但Mo和W的结构特征很少的氰基-过氧配合物。[W中的过氧部分的侧向配位模式通过X射线晶体结构测定[d（OO）＝ 1.41A；（CN）7（eta2-O2）] 3-确定。peroxo咬合角度：41.0度]并通过振动光谱法证实[nu（OO）= 915 cm（-1）]。络合物离子具有梯形十三面体的几何形状，代表具有一二齿和七个单齿配体的新型九坐标络合物。循环伏安法显示[W（CN）7（eta2-O2）] 3-在CH3CN中具有可逆的氧化还原行为，其标准还原电位等于1.130V。通常，对大气中氧气的兴趣源自该分子作为配体的多
• The oxidation of thiosulphate ions by octacyanotungstate(V) in weak acidic medium
  作者：C.R. Dennis、J.G. Leipoldt、S.S. Basson、G.J. Lamprecht

  DOI：10.1016/s0277-5387(00)87238-1

  日期：1985.1

  The kinetics of the oxidation of thiosulphate ions by octacyanotungstate(V) ions has been studied in the pH range 3.9–5.0. The reaction showed zero-order kinetics with respect to [W(CN)83−] and is consistent with the rate law R = k[H+][S2O32−]2. A reaction mechanism is proposed for the reaction with a third-order rate constant of 0.26 M−2 s−1 at 25°C.

  在pH值3.9-5.0范围内，已研究了八硫基钨酸根（V）离子氧化硫代硫酸根离子的动力学。所述反应显示零级动力学相对于[W（CN）8 3- ]，并且与速率法相一致- [R = ķ [H + ] [S 2 ö 3 2- ] 2。提出了在25℃下以0.26M -2 s -1的三阶速率常数进行反应的反应机理。
• Spectrophotometric determination of the reaction stoichiometry of the reduction of octacyanotungstate(V) by hydroxylamine in acidic and basic media
  作者：J.H. Potgieter

  DOI：10.1016/s0277-5387(00)80359-9

  日期：1989.1

  The stoichiometry of the reduction of octacyanotungstate(V) by hydroxylamine in basic and acidic media has been studied by a spectrophotometric technique. It was found that the stoichiometric ratio between W(CN)83− and hydroxylamine was 2 : 1 in a basic medium and 1 : 1 in an acidic medium, in agreement with previously proposed values.

  通过分光光度法研究了碱性和酸性介质中羟胺还原八碳烯基非钨酸盐（V）的化学计量。已经发现，W（CN）8 3-和羟胺之间的化学计量比在碱性介质中为2：1，在酸性介质中为1：1，与先前提出的值一致。
• Photochemistry of aqueous [W(CN)8]4−
  作者：A.E. Nya、Hari Mohan

  DOI：10.1016/s0277-5387(00)88015-8

  日期：1984.1

  Aqueous [W(CN)8]4− undergoes photoaquation when irradiated at ∼ 365 nm with pH independent quantum yield. The yield for aquoheptacyanotungstate (IV) ion production is 0.8 at 0.5°C. If added alkali is present a wide variety of products [W(CN)7(OH)]4−, [WO2(CN)4]4−, [WO(OH)(CN)4]3− [W(OH)2(CN)4]2− are formed.

  [W（CN）8 ] 4−水溶液在〜365 nm处以pH无关的量子产率进行辐照。在0.5℃下，七庚基非钨酸根（IV）离子的产量为0.8。如果存在添加的碱，则存在多种产品[W（CN）7（OH）] 4−，[WO 2（CN）4 ] 4−，[WO（OH）（CN）4 ] 3− [W（OH） ）2（CN）4 ] 2-形成。