New ferrocenyl dendritic macromolecules based on flexible poly(propylenimine) dendrimer cores, built up to the fifth generation, containing 4, 8, 16, 32, and 64 peripheral ferrocenyl moieties, have been prepared and characterized. Solution electrochemical studies showed that all the ferrocenyl redox centers attached to the dendritic surface are electrochemically independent and that, in CH2Cl2 and THF as solvents, the neutral dendrimers undergo oxidative precipitation onto the electrode surfaces.

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A new class of ferrocenyl and permethylferrocenyl polymers 2 and 3, containing a cyclotetrasiloxane in the backbone, has been prepared via hydrosilylation reactions. The synthesis of the tetranuclear model l,3,5,7-tetrakis(ferrocenylethyl)-l,3,5,7-tetramethylcyclotetrasiloxane (1) is also reported. The different nature of the cyclopentadienyl ring substituents was found to have influence on the electrochemical behavior of solutions and of electrode surfaces modified with electrodeposited films of these polymers.Macromolecular systems containing organometallic units are of increasing interest as a result of their unique properties.1 Ferrocenyl-based polymers2 are useful materials for modification of electrodes, as electrochemical biosensors,3 and as nonlinear optical systems.20 As a part of our ongoing studies on the chemistry of silicon-containing organometallic compounds, we recently synthesized new classes of macromolecules containing ferrocenyl moieties together with polyhedral octasilsesquioxanes,4 linear siloxanes,5 or organosilicon dendrimers.6 Now we have extended our studies to systems that contain cyclosiloxanes as frameworks of silicon atoms. Due to their stereochemical properties, organometallic-substituted cyclosiloxanes are potential candidates as sterically controlled multifunctional catalyst systems. Although several examples of metallocarbonyl-substituted cyclosiloxanes have been