Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M 2 Ru 3 (M=Fe, Ru)

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Abstract In this work, we report the design and synthesis of two chain‐like pentanuclear cyanido‐bridged complexes trans ‐[Ru(bpy) 2 (μ‐CN) 2 ][ cis ‐Ru(bpy) 2 (μ‐NC)M(dppe)Cp*] 2 [PF 6 ] 4 (M=Fe, 1 4+ ; M=Ru, 2 4+ ) and the electronic communication properties of their oxidized products 1 m+ (m=6, 7, 8) and 2 n+ (n=5, 6, 7, 8). The single‐crystal X‐ray diffraction analysis of 1 m+ (m=4, 6, 7) and 2 4+ show that 1 4+ and 2 4+ possess a Z‐type array structure, 1 7+ is a U‐type one, and 1 6+ exhibits both the types. The investigations indicate that both 1 and 2 show an extraordinarily strong electronic interaction between the two side Ru across the central NC−Ru−CN, leading to the formation of a fully delocalized cyanidometal Ru−Ru−Ru bridge for both three‐electron oxidized states 1 7+ and 2 7+ . Moreover, it should be noted that in 1 there exists no electronic interaction between the two terminal Fe ions. Upon substitution of Fe by Ru, however, 2 exhibits an electronic interaction between the two terminal metal ions across the trinuclear cyanidometal CN−Ru−NC−Ru−CN−Ru−NC bridge which is up to 20 Å.

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