Alumazene adducts with triphenylphosphine oxide

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Authors

LÖBL Jiří NEČAS Marek PINKAS Jiří

Year of publication 2006
Type Article in Periodical
Magazine / Source Main Group Chemistry
MU Faculty or unit

Faculty of Science

Citation
Field Inorganic chemistry
Keywords Alumazene; Single-crystal X-ray diffraction; Iminoalane; Triphenylphosphine oxide; Lewis acid-base adducts
Description 1,3,5-trimethyl-2,4,6-tris(2,6-diisopropylphenyl)alumazene [2,6-(i-Pr)2C6H3NAlMe]3, (1) is a benzene-like iminoalane with a planar hexagonal (Al-N)3 core. The aluminum centers are highly Lewis acidic due to the low delocalization of nitrogen lone pairs. We examined the alumazene ability to form acid-base adducts with triphenylphosphine oxide. Both monoadduct, 1(OPPh3), (2) and bisadduct 1(OPPh3)2, (3) were prepared, isolated, and spectroscopically characterized. Their molecular structures were determined by the single-crystal X-ray diffraction method. The monoadduct 2 displays a boat conformation of the central ring with very short Al[sbnd]N bonds (1.779, 1.769(2) A). The bisadduct 3 features the expected trans geometry in contrast to the previously reported bisadduct cis-1[OP(OMe)3]2. A different behavior of 2 and 3 in solution was observed by NMR spectroscopy. The monoadduct 2 is stable to dissociation while 3 shows signal broadening by chemical exchange because of the weakening of the second coordination Al[sbnd]O bond and/or internal rotation.
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