Homoleptic 1-norbornyl complexes of group 4 and manganese: synthesis, structures, volatility, and thermal stability

Detailed syntheses are reported for the previously reported homoleptic 1-norbornyl complexes [M(norb) 4 ] {M = Ti (1), Zr (3), Hf (4), and Mn (5)}. These compounds were characterized by combustion elemental analysis, NMR spectroscopy, single crystal X-ray diffraction (for 1 and 3), and SQUID magnetometry (for 5). The reaction by-product [{(norb) 3 Ti} 2 (μ-O)] (2) was also spectroscopically and structurally characterized. To assess the potential viability of 1 and 3–5 as precursors for thin film deposition by CVD or ALD, their volatility and thermal stability were evaluated by sublimation, thermogravimetric analysis, and in the case of 4, bulk thermolysis.