Electronically Active Cyclocarborane-Metal-Arene Assemblies

The designed synthesis of stable, soluble macromolecular complexes incorporating MC2B3 subunits in which M is a transition metal was explored in detail, with emphasis on 1 the efficient preparation of viable building-block molecules such as CpCoEt2C2B3H5 Cp Eta5-C5Me5 2 the derivatization and tailoring of these via attachment of substituents including organic functional groups to the carborane rings 3 the construction of multidecker stacks via a novel metal-promoted stacking process 4 the linkage of stacked sandwiches via coupling, fusion, and other methods and 5 initial studies on the preparation of electroactive or magnetoactive solid state materials from metallacarborane precursors. The synthesis of novel metallacarborane sandwiches that are direct structural analogues of metallocenes, and mixed-sandwich salts of the type Cp2M Et2C2Bn2M in which M and M are transition metals was also achieved. Detailed studies of the molecular and electronic structures of many of the above systems were conducted via NMR, ESR, X-ray crystallography, and electrochemical methods. Carboranes, Metal-arene complexes, Macromolecules, Organometallic polymers, Metallacarboranes, Sandwich complexes, Cobaltacarboranes, Multidecker sandwich complexes.