An investigation of possible photolysis and thermolysis effects in metal atom cocondensation procedures. Crucible insulation effects on metal atom oxidative addition, alkene isomerization and polymerization, and the discovery of homogeneous metal-polymer solutions.

Abstract During metal atom cocondensation procedures, the metal vaporization sources operate about 1220–1800°C emitting a great deal of light. Insulation of these crucibles effectively cuts down heat and light emission, but also adds greatly to the surface area where thermolysis reactions may occur. The effect of crucible insulation has been studied in an oxidative addition reaction (Pd + C 6 H 5 CH 2 Cl), alkene isomerization (Ni + alkenes), and alkenes polymerizations (Ni + styrene and tetrafluoroethylene). Our findings indicate that the effect of wool insulators (Kaowool or Fiberfrax) is not a photolytic effect, but a pyrolysis effect. This pyrolysis causes production of organic free radicals from the substrate, and these radicals cause destruction of C 6 H 5 CH 2 PdCl, isomerization and polymerization of alkenes. No effects attributable to photolysis or matrix warming in the absence of insulator were found. Thus, the presence of wool insulators caused polymerization and isomerization reactions to be several fold greater in importance. During the course of this work we discovered that homogeneous Ni-polystyrene solutions could be produced, and this has proven to be a selective nickel catalyst worthy of further study.