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DOI: 10.1039/A605177D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 99-104

Synthetic, structural, electrochemical and electronic characterisation of heterobimetallic bis(acetylide) ferrocene complexes

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Michael C. B. Colbert, Jack Lewis, Nicholas J. Long, Paul R. Raithby, Andrew J. P. White and David J. Williams

Abstract

A series of novel heterobimetallic bis(acetylide) ferrocene complexes featuring a bis[1,2-bis(diphenylphosphino)methane]ruthenium centre and seven variously substituted aromatic acetylene ligands have been synthesised and characterised. The crystal structure of trans-[Ru(dppm)2{C[triple bond, length as m-dash]C(C5H4 )Fe(C5H5[hair space])}2[hair space]] shows the ruthenium centre in a distorted-octahedral environment bound to two ferrocene units in a linear fashion by ‘rigid-rod’-like acetylene linkages. The conformation is stabilised by strong intramolecular CH·[thin space (1/6-em)]·[thin space (1/6-em)]·π(C[triple bond, length as m-dash]C) interactions. Electrochemical studies showed that incorporation of donor-substituted aromatic acetylide ligands causes a cathodic shift in the RuII/III redox potential. Conversely, an anodic shift is observed when electron-withdrawing substituents are present in the acetylide systems. Electronic spectral measurements indicated that the systems belong to the Robin and Day ‘Class II’ mixed-valence species and suggest that greater electronic interaction occurs in the bis(acetylide) complexes than in the corresponding monoacetylide chloro-complex.

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