Mechanisms of pyrolysis of organometallic deposition precursors

The gas-phase pyrolysis mechanisms of a number of potential transition-metal deposition precursors have been investigated using the techniques of: (i) infrared laser powered homogeneous pyrolysis coupled with product identification by FTIR, NMR and GC-MS; (ii) stirred Flow Reactor kinetic measurements; (iii) EPR spectroscopy of matrix-isolated free radicals. Preliminary results are presented for: (a) MeMn(CO)5 and AcMn(CO)5, both alone and in the presence of Me3SiH; (b) C5H5Mn(CO)3 and MeC5H4Mn(CO)3; (c) C4H6Fe(CO)3; and (d)(C5H5)2Fe, all of which provide clear evidence that purely homogeneous pathways can be very different from those of surface-catalysed decomposition.