Self-assembly of arene ruthenium acylpyrazolone fragments to tetranuclear metallacycles. Molecular structures and solid-state N-15 CPMAS NMR correlations

摘要

Reactions of [(eta(6)-cymene)Ru(mu-Cl)C](2) with acylpyrazolone ligands HO' (HQ' in general; in detail, HQ(CH2Cl) = 2-ch loro-1(5-hydroxy-methyl-1-phe pyrazol-4-ypethanone), HQ(hex) = 1- (5- hydroxy-3-methyl-l-phenyl-1H-pyrazol-4-yOheptan-1-one), = 1-15- hydroxy-3-methyl-1-phenyl-1Hpyrazol-4-y11-3,3-dimethylbutan-l-one)), in the presence of base, gave the corresponding [(q(6)-cymene) Ru(a)C11 mononuclear complexes. They react with AgX (where X = O3SCF3 or BF4) in dry acetone affording cationic metalla-cycles (eta(6)-cymene)Ru(CO14(X)(4). The complexes were fully characterized by analytical and spectroscopic methods and the solid-state structures of mononuclear and tetranuclear complexes have been determined by single-crystal X-ray diffraction. The hapticity of the acylpyrazolone ligands to the Ru metal centre has also been established by C-13 and N-15 CPMAS NMR spectroscopy for the complexes where the lack of crystallinity prevented the elucidation of the crystal structure by SCXRD data.