期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 10, 期 24, 页码 6402-6410出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400496
关键词
ligand effects; N ligands; noncovalent interactions; rearrangement; ruthenium
A Ru-11 complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with beta-diketones gave beta-diketonato complexes in which hydrophobic pi-pi or CH/pi interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric beta-diketone benzoylace-tone, an isomer with a CH/pi interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-beta-diketonato coordination bonds (activation energy 52 kJmol(-1)). This indicates that CH/pi interactions can be more favored thermodynamically than pi-pi interactions in a suitable hydrophobic environment.
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