Fulvalenediyl-bridged heterobimetallic complexes consisting of sandwich and half-sandwich compounds with early–late transition metals

A straightforward synthesis methodology for the preparation of heterobimetallic [(η5-C5H5)(η5-C5H4-C5Me4)M] (3a, M = Fe; 3b, M = Ru) and [(η5-C5H5)((μ-η5:η5-C5H4-C5Me4)TiCl3)M] (4a, M = Fe; 4b, M = Ru) in which early and late transition metals are connected by a fulvalenediyl bridge is reported.The structures of molecules 3b and 4a in the solid state are discussed. Most noteworthy in 4a is the exo arrangement of the iron and titanium atoms coordinated by the fulvalenediyl unit which itself is twisted with a dihedral angle between the joined cyclopentadienyl rings of 19.33(9)°. Electrochemical, UV/Vis/NIR spectroscopic and spectroelectrochemical experiments on 4a and Cp∗TiCl3, for comparison, provide evidence for some transfer of electronic information between the conjoined ferrocene and half-sandwich titanocene trichloride subunits of 4a. Evidence comes from systematic potential shifts and the presence of a fairly intense Fe → Ti charge-transfer absorption band that vanishes upon oxidation and reduction of 4a.

Graphical abstractA straightforward synthesis methodology to prepare heterobimetallic complexes with early and late transition metals of type [(η5-C5H5)(η5-C5H4-C5Me4)M] and [(η5-C5H5)((μ-η5:η5-C5H4-C5Me4)TiCl3)M] (M = Fe, Ru) is described. These fulvalenediyl bridged complexes were characterized and the electrochemical and spectroelectrochemical behavior of 4a is reported.Figure optionsDownload full-size imageDownload as PowerPoint slide