Syntheses and crystal and molecular structures of hexaaquaruthenium(II) p-toluenesulfonate and hexaaquaruthenium(III) p-toluenesulfonate, [Ru(H2O)6](C7H7SO3)2 and [Ru(H2O)6](C7H7SO3)3.3H2O
Syntheses and crystal and molecular structures of hexaaquaruthenium(II) p-toluenesulfonate and hexaaquaruthenium(III) p-toluenesulfonate, [Ru(H2O)6](C7H7SO3)2 and [Ru(H2O)6](C7H7SO3)3.3H2O
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对甲苯磺酸六水钌(II)和对甲苯磺酸六水钌(III)[Ru(H2O)6](C7H7SO3)2和[Ru(H2O)6](C7H7SO3)3.3H2O的合成、晶体和分子结构
DOI：
10.1021/ic00141a016
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发表时间：
1982
影响因子：
4.6
通讯作者：
A. Ludi
中科院分区：
文献类型：
--
作者：
P. Bernhard;H. Buergi;J. Hauser;H. Lehmann;A. Ludi
Ru（H2O）6（tos）2（II）（tos”是对甲苯磺酸盐）的晶体从Ru（H2O）62+水溶液生长，所述Ru（H2O）62+水溶液通过用金属铅还原Ru O 4溶液获得。Ru（H2O）6（tos）3·3 H2O（III）的晶体由Ru（H2O）63+水溶液生长，所述Ru（H2O）63+水溶液通过用O2氧化Ru（H2O）62+溶液获得。Ⅱ的空间群为PI，晶胞参数a= 6.138（1）A，B= 7.287（2）A，c= 12.423（4）A，a= 92.22（2），ε = 94.82（2），ε = 107.13（2），Z= 1。对于III，空间群为C2/c，晶格常数a= 25.466（7）A，B= 7.235（4）A，c= 35.113（8）A，ε = 93.97（2），Z= 8。Ⅱ的结构在2302个反射峰中精确到R= 3.3%，Ⅲ的结构在2989个反射峰中精确到R= 5.2%，F_0>（0）。在两种结构中，Ru（H_2G）_6八面体都通过氢键与阴离子的SO_3基团相连，OH-O距离为~ 2.5 ~ 3.0。Ru（II）-OH 2的平均金属-氧距离为2.122（16）A，Ru（III）-OH 2的平均金属-氧距离为2.029（7）A。讨论了键长变化对Ru（H2O）63+/2+自交换反应速率的影响。
Crystals of Ru (H20) 6 (tos) 2 (II)(tos" is p-toluenesulfonate) were grown from aqueous Ru (H20) 62+ solutions obtained by reduction of Ru04 solutions with metallic lead. Crystals of Ru (H20) 6 (tos) 3-3H20 (III) were grown from aqueous Ru (H20) 63+ obtained by oxidation of a Ru (H20) 62+ solution with 02. For II the space group is PI withcell parameters a= 6.138 (1) A, b= 7.287 (2) A, c= 12.423 (4) A, a= 92.22 (2), ß= 94.82 (2),= 107.13 (2), and Z= 1. For III the space group is C2/c with lattice constants a= 25.466 (7) A, b= 7.235 (4) A, c= 35.113 (8) A, ß= 93.97 (2), and Z= 8. The structure of II was refined to R= 3.3% for 2302 reflectionswith Fa>(0); the structure of III, to R= 5.2% for 2989 reflections with F0>(0). In both structures Ru (H2G) 6 octahedra are linked by hydrogen bonds to the S03 groups of the anion, the OH—O distances rangingfrom~ 2.5 to 3.0 A. The average metal-oxygen distance is 2.122 (16) A for Ru (II)-OH2 and 2.029 (7) A for Ru (III)-OH2. The effect of the change in bond length on the rate of the Ru (H20) 63+/2+ self-exchange reaction is discussed.