Crystal Structure of Mixed-valence Compound 1′,1'″-Dipropylbiferrocenium Triiodide with Averaged-valence Type Irons at 298 K and with Trapped-valence Type Irons at 110 K and Thermal Electron Transfer Process of Mono-oxidized Binuclear Ferrocene Derivatives
Crystal Structure of Mixed-valence Compound 1′,1'″-Dipropylbiferrocenium Triiodide with Averaged-valence Type Irons at 298 K and with Trapped-valence Type Irons at 110 K and Thermal Electron Transfer Process of Mono-oxidized Binuclear Ferrocene Derivatives
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298 K 平均价型铁和 110 K 俘获价型铁混合价化合物 1,1-二丙基联二茂铁三碘化物的晶体结构及单氧化双核二茂铁衍生物的热电子传递过程
DOI：
10.1246/bcsj.55.2327
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发表时间：
1982
影响因子：
4
通讯作者：
S. Iijima
中科院分区：
文献类型：
--
作者：
M. Konno;Shinaki Hyodo;S. Iijima
通过X射线衍射测定了1′，1“”-二丙基双二茂铁（PrFcFcPr）+I3−的晶体结构，其在298 K时显示平均价态铁，在110 K时显示捕获价态铁。晶体在298 K为三斜晶系，空间群为P\bar 1，a=8.5148（8），B=8.5482（5），c=10.9032（13）A，α=89.546（9），β=115.582（9），γ=108.488（7）°，U=671.10（9）A3，Z=1。晶体在110 K为三斜晶系，空间群P1，a=8.431（2），B=8.478（2），c=10.816（3）A，α=88.58（3），β=117.39（2），γ=108.65（2）°，U=643.4（3）A3，Z=1。在298 K和110 K下，结构被精修至R=0.042和R=0.050。在298 K时，阳离子（PrFcFcPr）+位于对称中心，两个Fc单元在晶体学上是等价的，而在110 K时，对称中心丢失，二茂铁样和二茂铁样Fc单元被区分开。在110 K时，碘原子与阳离子之间形成了三维氢键网络，而在298 K时，碘原子与阳离子之间形成了三维氢键网络。1′，1“”-二乙基-和1′，1“”-二丙基联二茂铁的红外光谱
The crystal structure of 1′,1'″-dipropylbiferrocenium (PrFcFcPr)+I3−, which shows averaged-valence irons at 298 K and trapped-valence irons at 110 K, was determined by X-ray diffraction. The crystal at 298 K is triclinic, space group P\bar1, a=8.5148(8), b=8.5482(5), and c=10.9032(13) A, α=89.546(9), β=115.582(9), and γ=108.488(7)°, U=671.10(9) A3, and Z=1. The crystal at 110 K is triclinic, space group P1, a=8.431(2), b=8.478(2), and c=10.816(3) A, α=88.58(3), β=117.39(2), and γ=108.65(2)°, U=643.4(3) A3, and Z=1. Structures were refined to R=0.042 at 298 K and R=0.050 at 110 K. At 298 K cation (PrFcFcPr)+ sits on the symmetry center and the two Fc units are crystallographically equivalent, whereas at 110 K the symmetry center is lost and ferrocene-like and ferrocenium-like Fc units are distinguished. A three-dimensional hydrogen-bond network is clearly found between the cation and iodine atoms at 110 K, in contrast to the result at 298 K. Infrared spectra of 1′,1'″-diethyl- and 1′,1'″-dipropylbiferrocen...