Insights into the Thermal Decomposition Mechanism of Molybdenum(VI) Iminopyridine Adducts

Understanding the thermal behavior of vapor phase precursors is important to assess their potential for thin film deposition processes and to discern decomposition pathways. Here we present a series of dichloromolybdenum(VI) compounds on three different frameworks: the bis(alkylimido)-, dioxo- and mono(alkylimido)mono(oxo), which is the first foray into understanding the potential differences of decomposition mechanisms for molecules using these strongly bonded ligands. We report the synthesis of three novel metal complexes which have been fully characterized by spectroscopic techniques as well as single-crystal X-ray diffraction (SCXRD) and thermal analysis. Through in situ thermolysis reactions, we show the decomposition of all compounds generates the free N, N ′-chelate ligand. Further thermal decomposition deviated from previously reported γ-H elimination, showing that the presence of β-hydrogens in the complexes provided alternative low-temperature decomposition pathways.