Alumazene Adducts with Pyridines: Synthesis, Structure, and Stability Studies
| Authors | |
|---|---|
| Year of publication | 2007 |
| Type | Article in Periodical |
| Magazine / Source | INORGANIC CHEMISTRY |
| MU Faculty or unit | |
| Citation | |
| Field | Inorganic chemistry |
| Keywords | Lewis acid-base; adducts; alumazene; pyridine |
| Description | Lewis acid-base adducts of the alumazene [2,6-(i-Pr)2C6H3NAlMe]3 (1) with pyridine (py) and 4-dimethylaminopyridine (dmap) were synthesized and structurally characterized: 1(py)2 (2), 1(py)3 (3), 1(dmap)2, (4), and 1(py)(dmap) (5). The bisadducts 2, 4, and 5 form the trans isomers. The trisadduct 3 exhibits an unexpected cis-cis isomer and can be prepared only in the presence of excess py. The planarity of the alumazene ring is lost upon coordination of the Lewis base molecules. A comparison of the Al-N(base) bond distances and pyramidality at Al suggests the higher basicity of dmap. NMR spectroscopy confirms stability to dissociation of the bisadducts in solution while the trisadduct 3 is labile and converts to 2. The thermodynamics of the adduct formation has been investigated experimentally and theoretically. Thermodynamic characteristics of the 1(py)n (n = 2, 3) dissociation reactions in the temperature range 25-200 oC have been derived from the vapor pressure-temperature dependence measurements by the static tensimetric method. In all experiments excess py was employed. Quantum chemical computations at the B3LYP/6-31G* level of theory have been performed for the 1(py)n and model complexes [HAlNH]3(py)n (n = 1-3). Obtained results indicate that for the gas phase adducts upon increasing the number of py ligands the donor-acceptor Al-N(py) distance increases in accord with decreasing donor-acceptor bond dissociation energies. |
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