Premium
Intramolecular Rearrangement for Regioselective Complexation by Intramolecular CH/π Interaction in a Hydrophobic Cavity of a Ruthenium Coordination Sphere
Author(s) -
Kojima Takahiko,
Miyazaki Soushi,
Hayashi Kenichi,
Shimazaki Yuichi,
Tani Fumito,
Naruta Yoshinori,
Matsuda Yoshihisa
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400496
Subject(s) - intramolecular force , chemistry , ruthenium , regioselectivity , coordination sphere , hydrophobic effect , nuclear magnetic resonance spectroscopy , spectroscopy , stereochemistry , photochemistry , crystallography , medicinal chemistry , catalysis , crystal structure , organic chemistry , physics , quantum mechanics
A Ru II complex with a hydrophobic cavity formed from two 1‐naphthoylamide groups was prepared. Its reactions with β‐diketones gave β‐diketonato complexes in which hydrophobic π–π or CH/π interactions were confirmed by NMR spectroscopy and X‐ray crystallography. In the case of the asymmetric β‐diketone benzoylacetone, an isomer with a CH/π 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 Ruβ‐diketonato coordination bonds (activation energy 52 kJ mol −1 ). This indicates that CH/π interactions can be more favored thermodynamically than π–π interactions in a suitable hydrophobic environment.