Synthesis, Characterization, and Thermal Properties of N-alkyl β-Diketiminate Manganese Complexes

A series of N, N'-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vapor-phase film growth processes. Bis( N, N'-dimethyl-4-amino-3-penten-2-imine) manganese(II), 1, and bis( N- N'-diisopropyl-4-amino-3-penten-2-imine) manganese(II), 2, specifically, emerge as the most promising candidates, balancing volatility (sublimation temperatures < 100 °C at 100 mTorr) with coordinative unsaturation and reactivity, as revealed by rapid release of ligand in the presence of a silica surface. Good correlation is observed between buried volume calculations and relative surface reactivity data, indicating that metal availability resulting from sterically open ligand alkyl substituents increases surface reactivity. The thermal stability, volatility, and reactivity exhibited by these compounds render them promising precursors for the growth of manganese oxide films via vapor-phase growth processes.