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Investigation of the electron transfer properties between metal centers in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration.

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To investigate the electron transfer properties between metal centers and their influencing factors in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration, binuclear cis-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)2(μ-CN)][PF6]n (cis-1[PF6]n, n = 1, 2)… Click to show full abstract

To investigate the electron transfer properties between metal centers and their influencing factors in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration, binuclear cis-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)2(μ-CN)][PF6]n (cis-1[PF6]n, n = 1, 2) and trinuclear cis/trans-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)2(μ-CN)Fe(dppe)Cp][PF6]n (cis/trans-2[PF6]n, n = 2, 3, 4) (Cp = 1,3-cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, 5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridyl) cyanido-bridged complexes were synthesized and well characterized. The experimental results indicate that the presence of the other terminal fragment Cp(dppe)FeIII in cis-2[PF6]4 results in higher MMCT energy than that of cis-1[PF6]2. In addition, the trans-configuration is more conducive to electron transfer between metal centers than the cis-configuration in trinuclear cyanido-bridged mixed valence complexes. Moreover, these mixed valence complexes cis-1[PF6]2 and cis/trans-2[PF6]n (n = 3, 4) could be assigned to Class II systems according to Robin and Day.

Keywords: valence complexes; cyanido bridged; cis; mixed valence; cis trans

Journal Title: Dalton transactions
Year Published: 2022

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