Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States.
Inorg Chem. 2010 Dec 20;49(24):11525-31. doi: 10.1021/ic101628z. Epub 2010 Nov 11.
Previously, the synthesis of compounds Ru(2)(D(3,5-Cl(2)Ph)F)(4-n)(O(2)CFc)(n)Cl (n = 1, 3a; 2, 4a), where D(3,5-Cl(2)Ph)F is N,N'-di(3,5-dichlorophenyl)formamidinate, from the carboxylate exchange reactions between Ru(2)(D(3,5-Cl(2)Ph)F)(4-n)(OAc)(n)Cl and ferrocene carboxylic acid was communicated. Reported herein is the preparation of analogous compounds Ru(2)(DmAniF)(4-n)(O(2)CFc)(n)Cl (n = 1, 3b; 2, 4b), where DmAniF is N,N'-di(3-methoxyphenyl)formamidinate, from Ru(2)(DmAniF)(4-n)(OAc)(n)Cl. Compounds 3 and 4 were characterized with various techniques including X-ray structural determinations of 3a and 4a. Voltammetric behaviors of compounds 3 and 4 were investigated, and stepwise one-electron ferrocene oxidations were observed for both compounds 4a and 4b. Spectral analysis of the monocations 4 indicated that they are the Robin-Day class II mixed valent Fc···Fc species. Measurement and fitting of magnetic data (χT) of 4a between 2 and 300 K revealed a typical zero-field splitting of a S = 3/2 center with D = 77 cm(-1), while those of [4a]BF(4) are consistent with the presence of S = 3/2 (Ru(2)) and S = 1/2 (Fc(+)) centers that are weakly coupled (zJ = -0.76 cm(-1)).
先前，通过羧酸根交换反应，从 Ru(2)(D(3,5-Cl(2)Ph)F)(4-n)(OAc)(n)Cl（n = 1,3a;2,4a）合成了化合物 Ru(2)(D(3,5-Cl(2)Ph)F)(4-n)(O(2)CFc)(n)Cl（n = 1,3a;2,4a），其中 D(3,5-Cl(2)Ph)F 是 N,N'-二（3,5-二氯苯基）甲脒基。本文报道了从 Ru(2)(DmAniF)(4-n)(OAc)(n)Cl（n = 1,3b;2,4b）制备类似化合物的方法，其中 DmAniF 是 N,N'-二（3-甲氧基苯基）甲脒基。化合物 3 和 4 通过各种技术进行了表征，包括 3a 和 4a 的 X 射线结构测定。研究了化合物 3 和 4 的伏安行为，观察到了化合物 4a 和 4b 的分步单电子 ferrocene 氧化。4的光谱分析表明，它们是 Robin-Day 类 II 混合价Fc···Fc物种。4a 在 2 到 300 K 之间的磁数据（χT）的测量和拟合表明，它具有典型的 S = 3/2 中心的零场分裂，D = 77 cm(-1)，而[4a]BF(4)的磁数据则与 S = 3/2（Ru(2)) 和 S = 1/2（Fc(+)) 中心的存在一致，这些中心之间的弱耦合（zJ = -0.76 cm(-1))。
