State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
Dalton Trans. 2012 Oct 21;41(39):12163-9. doi: 10.1039/c2dt30614j.
Treatment of trans-(Ph-tpy)Ru(PPh(3))(CN)(2) (Ph-tpy = 4'-phenyl-2,2':6',2''-terpyridine, PPh(3) = triphenylphosphine) with 2 equiv of Cp(dppe)Fe(NCCH(3))Br (dppe = bis(diphenylphosphino)ethane) in the presence of NH(4)PF(6) produced a trinuclear cyanide-bridged complex, trans-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh(3))(CN)Fe(dppe)Cp]PF(6) (1PF(6)). Its one-electron oxidation product (1PF(6)) and two-electron-oxidation product (1PF(6)) were obtained by oxidation with (Cp)(2)FePF(6) and AgPF(6), respectively. Firstly, the crystal structures of the cyanide-bridged complexes with three stable states were fully characterized. The reversible electrochemistry measurement of 1(2)(+) shows the presence of a long range intervalence interaction between the external iron centres. Both 1(3)(+) and 1(4)(+) were considered to be Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis indicated the presence of a moderately strong antiferromagnetic coupling between the two remote Fe(III) ions across the Fe-NC-Ru-CN-Fe array in 1(4)(+). This proves that the Ru(II)-dicyano complex is a bridging ligand that can transmit electro- and magneto-communication.
用 2 当量的 Cp(dppe)Fe(NCCH(3))Br（dppe = 双（二苯基膦）乙烷）处理反式-(Ph-tpy)Ru(PPh(3))(CN)(2)（Ph-tpy = 4'-苯基-2,2':6',2''-三联吡啶，PPh(3) = 三苯基膦），并在 NH(4)PF(6)存在下，生成了一个三核氰桥联配合物，反式-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh(3))(CN)Fe(dppe)Cp]PF(6)（1PF(6)）。其单电子氧化产物（1PF(6)）和双电子氧化产物（1PF(6)）分别通过用(Cp)(2)FePF(6)和 AgPF(6)氧化得到。首先，对具有三种稳定状态的氰桥联配合物的晶体结构进行了充分表征。1(2)(+)的可逆电化学测量表明，外部铁中心之间存在长程间隔相互作用。根据 Robin 和 Day 的分类，1(3)(+)和 1(4)(+)都被认为是二类混合价态配合物。磁性分析表明，在 1(4)(+)中，两个远程 Fe(III)离子之间存在中等强度的反铁磁耦合，通过 Fe-NC-Ru-CN-Fe 阵列。这证明 Ru(II)-二氰基配合物是一种可以传递电和磁通讯的桥联配体。
