Insights into\nthe Thermal Decomposition Mechanism\nof Molybdenum(VI) Iminopyridine Adducts

Understanding the thermal behavior of vapor phase precursors\nis\nimportant to assess their potential for thin film deposition processes\nand to discern decomposition pathways. Here we present a series of\ndichloromolybdenum(VI) compounds on three different frameworks: the\nbis(alkylimido)-, dioxo- and mono(alkylimido)mono(oxo), which is the\nfirst foray into understanding the potential differences of decomposition\nmechanisms for molecules using these strongly bonded ligands. We report\nthe synthesis of three novel metal complexes which have been fully\ncharacterized by spectroscopic techniques as well as single-crystal\nX-ray diffraction (SCXRD) and thermal analysis. Through <i>in\nsitu</i> thermolysis reactions, we show the decomposition of\nall compounds generates the free <i>N</i>,<i>N</i>′-chelate ligand. Further thermal decomposition deviated from\npreviously reported γ-H elimination, showing that the presence\nof β-hydrogens in the complexes provided alternative low-temperature\ndecomposition pathways.