Analysis of the Homogeneous Thermal Decomposition of the Tungsten Dimethylhydrazido Complex Cl₄(CH₃CN)W(NNMe₂) Using In Situ Raman Spectroscopy and DFT Calculations

Abstract

The gas-phase decomposition pathways of the tungsten dimethylhydrazido complexes Cl 4 (RCN)W(NNMe 2 ) (1a: R = CH 3 ; 1b: R = Ph), precursors for single source deposition of WN x C y , were investigated using a combination of experiments and calculations. Raman scattering experiments were performed in an impinging-jet, up-flow, aerosol-assisted CVD reactor to identify reaction intermediates.Density Functional Theory calculations (B3LYP/LanL2DZ) were used to estimate Raman active frequencies and explore the reaction surface.Dimethylamine and methylmethyleneimine, products from N-N cleavage of the hydrazido ligand, were observed under deposition conditions and identified by comparison with previously reported Raman shifts and calculated frequencies.