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Studies are conducted to devise methodologies as well as mechanisms for ring-opening polymerization (ROP) of strained [1]ferrocenophanes. It was found that the spontaneous ROP of tin-bridged [1]ferrocenophanes could be because of the presence of spurious trace quantities of Lewis basic or acidic impurities.

Synthesis of the first sulfur- and selenium-bridged [1]ferrocenophanes showed that these species have tilt angles of 31 degrees and 26 degrees respectively. Evidence for the high degree of ring strain was further provided by nuclear magnetic resonance chemical shifts of the ipso-carbon atoms in the [1]chalcogenaferrocenophanes. Data indicate that ring-opening polymerization reactions are less efficient in the formation of poly(ferrocenyl chalcogenides). Detailed studies of physical properties will be made when higher molecular weight samples of become available.

Three series of oligo(ferrocenylsilanes) were prepared and characterized with respect to their conformational, solid-state and electrochemical properties. The oligo(ferrocenylsilanes), which were synthesized via the anionic ring-opening oligomerization of the ferrocenophane Fe(eta-C5H4)2SiMe2, were of the type R-fc-(SiMe2-fc)(sub n-1)-R' where fc = Fe(eta-C5H4)2, R = R' when R' = H, and R = H when R' = SiMe3. Their synthesis, which proved the occurrence of oxidation at alternating iron sites, revealed the existence of an intervalence electron transfer absorption for partially oxidized oligo(ferrocenylsilanes).

Well-defined poly(ferrocenyldimethylsilanes) are prepared using the living anionic ring-opening polymerization (ROP) technique that had previously been used in preparing methylated silicon-bridged (1)ferrocenophane. The technique is also used to prepare various unique, well-defined organometallic/organic/inorganic multiblock copolymers constructed from various transition metals. Results indicate that living anionic ROP allows access to a variety of transition metal-containing polymers with controlled architectures.

Research is presented describing a new technique for the ring-opening polymerization of metallocenophanes at ambient temperature involving nucleophilic asistance by amines.

A method for transforming a two-component precursor system to active and selective vanadia-silica-zirconia heterogeneous catalysts for the oxidative dehydrogenation of propane is presented. The two components of the precursor system are OV[Oi(OBu)3]3 and Zr(OCMe2Et)4. Data derived from materials having a similar composition to the catalysts was used to test the molecular precursor route. Results showed that method is versatile, can control elemental composition and applicable to several catalyst formulations.

Synthesis of novel transition metal-containing block copolymers involves the living anionic ring-opening polymerization (ROP) of silicon-bridged (1)ferrocenophanes. Living anionic ROP helps prepare polymers with controlled structures and architectures and permits molecular weight control and end-group control. Living anionic ROP efficiently synthesize poly(ferrocenylsilane)-poly(dimethylsiloxane) block copolymers. Elemental analysis and multinuclear NMR experiments help characterize the structures of these copolymers.

An analysis of the reaction of ferrocenyllithium FcLi (Fc = Fe(eta-C5H4)(eta-C5H5)) with strained, ring-tilted silicon-bridged ferrocenophane which produces polymeric or oligomeric products based on the reactant's mole ratio reveals that anionic ring-opening polymerization of the ferrocenophane can provide oligomers and polymers of reasonable molecular weight. Peaks associated with a molecular ion and logical fragmentation products are evident in the mass spectrum of each oligomer.

Characterizes the first chalcogen-bridged [1] ferrocenophanes structurally and spectroscopically. Synthesis and characterization of the selenium and sulfur-bridged [1]-ferrocenophane; Electronic structure of [1]ferrocenophanes; Anionic and oligomerization of sulfur-bridged [1]ferrocenophane.