Oxidizing elemental platinum with oleum under harsh conditions: the unique tris(disulfato)platinate(IV) [Pt(S2O7)3]2- anion.
Oxidizing elemental platinum with oleum under harsh conditions: the unique tris(disulfato)platinate(IV) [Pt(S2O7)3]2- anion.
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在恶劣条件下用发烟硫酸氧化元素铂：独特的三(二硫酸根)铂酸(IV) [Pt(S2O7)3]2- 阴离子。
DOI：
10.1002/chem.201402086
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发表时间：
2014
期刊：
影响因子：
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通讯作者：
M. Wickleder
中科院分区：
文献类型：
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作者：
Jörn Bruns;T. Klüner;M. Wickleder
在碳酸钡的存在下，铂与硫酸（65% SO3）反应过程中，首次观察到单质铂被无机酸直接氧化为四价态。该反应在160℃的密封玻璃安瓿中进行，得到了Ba[Pt(S2O7)3](H2SO4)0.5(h2so7)0.5（三斜）的黄色单晶，P1， Z=2, a=992.05(2), b=1069.07(3), C =1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°，V=1033.95（5) Å(3)）。Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5的结构表现出独特的三（二硫）-铂酸阴离子[Pt(S2O7)3]（2-）的三个螯合二硫酸盐基团配位在铂原子上。电荷平衡是由Ba（2+）离子实现的，Ba（2+）离子由铂酸配合物中的（S2O7）（2-）基团以及无序硫酸和二硫酸分子配位。对大块材料进行热分解，发现分解残留物为元素铂和硫酸钡。
For the first time, direct oxidation of elemental platinum by a mineral acid to its tetravalent state was observed in course of the reaction of platinum with oleum (65 % SO3) in the presence of barium carbonate. The reaction has been carried out in torch-sealed glass ampoules at 160 °C and gave yellow single crystals of Ba[Pt(S2O7)3](H2SO4)0.5(H2S O7)0.5 (triclinic, P1, Z=2, a=992.05(2), b=1069.07(3), c=1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°, V=1033.95(5) Å(3)). The structure of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 exhibits the unique tris-(disulfato)-platinate anion [Pt(S2O7)3](2-) with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba(2+) ions, which are coordinated by (S2O7)(2-) groups from the platinate complex and by disordered sulfuric acids and disulfuric acid molecules. Thermal decomposition of the bulk material revealed elemental platinum and barium sulfate as decomposition residual.