The syntheses and characterizations of organometallic polymers from chromium and molybdenum complexes

Abstract

Derivatives of benzene chromium tricarbonyl, (116-arene)chromiumtricarbonyl, and a molybdenum complex, trans-bis(I,2-bis(diphenylphosphinoethane)bis(P-isocyanoaniline) molybdenum (0), were polymerized to form rigid organometallic polymer systems are reported. The resulting polymers were characterized systematically. The organochromium monomers were prepared by reacting the arene with chromium hexacarbonyl in refluxing dibutyl ether/tetrahydrofuran under inert conditions. There were several steps in the synthesis of the organomolybdenum monomer. p-Phenylenediamine was converted to p-isocyanoaniline in the presence of potassium hydroxide. Trans-bis(1,2-bis(diphenylphosphinoethane)bis(dinitrogen) molybdenum (0) was prepared by reducing molybdenum (V) chloride with a sodium/mercury amalgam in the presence of dinitrogen gas and bis(diphenylphosphinoethane) in tertrahydrofuran. Trans-bis(l ,2-bis(diphenylphosphinoethane)bis(dinitrogen) molybdenum (0) and pisocyanoaniline were reacted in tetrahydrofuran to prepare the organomolybdenum monomer,trans-bis(l ,2-bis(diphenylphosphinoethane)bis(p-isocyanoaniline) molybdenum (0). The syntheses and characterizations of model compounds and related organic polymers were attempted. Analogous model compounds and organic polymers were synthesized from isocyanates and acid chlorides in either dimethylacetamide or tetrahydrofuran. A series of organic polymers was synthesized via low temperature solution polycondensation from reacting diisocyanates and acid chlorides with the organometallic monomers in solution. An attempt to set up a gel permeation chromatography lab to determine the molecular weight of the polymers was unsuccessful. It is believed that the compounds formed from m-phenylenediamine, except for the monomer, have not been previously reported. The molybdenum polymers have not been reported. The organometallic polymers reduce the amount of hydrogen bonding of the polymers and increases the solubility of the polymers.