The synthesis of organometallic nanorods from molybdenum and tungsten diisonitrile complexes and a new method to synthesize air-stable sodium cyclopentadienide (NaCp) /

Abstract

Bis(diisonitrile) complexes were synthesized, characterized and are reported. The precursor to the bis(diisonitrile) complex, the bis(dinitrogen) complex, was synthesized by reducing the appropriate metal halide, MoCls or WCI6, with magnesium metal in the presence of two equivalents of a bidentate phosphine under an inert nitrogen atmosphere in THF. The bis(diisonitrile) complex was then synthesized by reacting the appropriate dintrogen metal complex with ten equivalents of 1,4-diisocyanobenzene or a derivative thereof. The solubility of these complexes was tuned via alkyl substituents on both the phosphine and the bis(diisonitrile) ligands although substitution on the phosphine had the greatest effect. The trimetallic isonitrile bridged complexes were then synthesized by combining the bis(diisonitrile) complex with two equivalents of cis( cyclooctene)pentacarbonylchromium(O). The trimetallic complexes exhibited an iridescent color denoting the presence of a highly conjugated x-system. The presence of this highly conjugated system implies that these complexes may posses electrical conductivity properties. A new, one-pot synthesis, of sodium cyclopentadienide, NaCp, is also reported. In this new method, dicyclopentadiene was cracked in a high-boiling, inert, non-polar solvent while sodium metal was being melted and finely divided in the same flask. The resulting CpH monomer then reacted with the finely divided sodium metal to produce NaCp, with precipitates out of the non-polar solvent. The NaCp that was produced shows remarkable stability towards air, is not pyrophoric like that produced by conventional methods, and does in fact have Cp ring-transfer capabilities as shown by the successful synthesis of ferrocene using the NaCp produced by this new one-pot method. Service crystallography of samples provided by Dr. Guy Crundwell of Central Connecticut State University is also reported.