화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.118, No.11, 2634-2643, 1996
Synthesis of a Novel Volatile Platinum Complex for Use in CVD and a Study of the Mechanism of Its Thermal-Decomposition in Solution
The synthesis, characterization, chemical vapor deposition, and mechanistic investigation of the thermal decomposition in aromatic solvents of cis-bis(eta(2),eta(1)-pent-4-en-1-yl)platinum (1) are described. Complex 1 has a unique chelated structure, giving rise to enhanced volatility, and has proved useful for the chemical vapor deposition of thin platinum films under mild conditions. Films deposited on a glass slide in a hot walled glass tube at 175 degrees C have an elemental composition of 82% Pt and 18% C. Kinetic, deuterium labeling, and chemical trapping experiments indicate that the decomposition of 1 in aromatic solvents proceeds by reversible beta-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant beta-deuterium isotope effect of k(H)/k(D) = 3.8 +/- 0.3. Added olefins are rapidly isomerized during the decomposition of 1; trapping experiments with diphenylacetylene indicate that intermediate 9 is the highly active catalyst that is responsible for the alkene isomerization.