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Volatile Heteroleptic Molybdenum Complexes: Synthesis, Structure, and Thermal Properties
Sung Kwang Lee1,2, Ji Yeon Ryu1, Bo Keun Park1
1Thin Film Materials Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon 34114, Republic of Korea.
None:
Molybdenum (Mo)-based thin films are widely applied in microelectronics and catalysis due to their electrical and thermal advantages. The development of suitable precursors for deposition of high-quality thin film is important. To resolve the problems of Mo(CO)6, we tried to dissociate carbonyl groups and introduce multidentate organic ligands. Mo(η3-allyl)(CO)2(MeCN)2Cl was used as a starting material to dissociate 4 CO groups from Mo(CO)6. We introduced tridentate-NNO ligands to dissociate a chloride and 2 MeCN. Finally, we synthesized new molybdenum complexes that can be expected to overcome the disadvantages owing to the carbonyl groups in Mo(CO)6. New heteroleptic molybdenum complexes, Mo(allyl)(CO)2(demamp) (1), Mo(allyl)(CO)2(demap) (2), Mo(allyl)(CO)2(demab) (3), Mo(crotyl)(CO)2(demamp) (4), Mo(allyl)(CO)2(demavp) (5), Mo(allyl)(CO)2(demaep) (6), and Mo(methallyl)(CO)2(demamp) (7), were synthesized by reactions of Mo(allyl)(CO)2(MeCN)2Cl with sodium salt of tridentate-NNO ligands in THF. Synthesized complexes were characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and single crystal X-ray diffraction. Thermal properties were investigated by thermogravimetric analysis (TGA). Especially, vapor pressure analysis was conducted to determine the vapor pressure of complex 4. We are sure that complex 4 is a potential candidate to apply as vapor-phase deposition precursor for molybdenum-containing thin films.
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