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Second sphere coordination behavior of aquo and amine ligands bound to a η-benzeneruthenium(II) cation
Authors:Hideo Kurosawa   Hideo Asano  Yoshiharu Miyaki
Affiliation:

Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565, Japan

Abstract:The bis(oxazoline) ligand, 2,2-bis[4(R)-phenyl-1,3-oxazolon-2-yl]propane (bpop), was introduced to the η6-benzenemthenium(II) moiety on treatment with [Ru(η6-C6H6)Cl2]2 to give [Ru(η6-C6H6)(bpop)Cl]+. Aquo and amine complexes [Ru(η6-C6H6)(bpop)(L)]2+ (L = H2O (1), NH2R; R = H (2) , Me (3) , and n-Bu (4) ) were prepared by treating the chloride complex with AgBF4 in the presence of L. X-ray structure determinations of 1 and 3 were carried out. Both complexes possessed a three-leg piano stool structure with the N or O donors located at the three comers of a pseudo octahedron. The aquo complex 1 exhibited a dynamic NMR feature in which two magnetically nonequivalent oxazoline parts observed at lower temperatures were interchanged with each other at higher temperatures. This observation was ascribed to the formation of a C2-symmetric 16-electron intermediate via Ru-OH2 cleavage, which is slower in acetone than in dichloromethane owing to more effective solvation by acetone around hydrogens of the coordinated water molecule. The two diastereotopic N-hydrogens of 4 underwent deuterium exchange with CD3OD with greatly different rates from each other owing to different energy of NHO (D) (CD3) interaction. Carboxylate and sulfonate ions (A) formed second sphere complexes with 4 by means of NHA hydrogen bonding, as evidenced by continuous shift of NH2 resonances with increasing amounts of the anions added.
Keywords:Second sphere coordination   Aquo complexes   Amine complexes   Ruthenium complexes   Benzene complexes
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