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

Abstract

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)3Ti}2(mu-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.