|Budget Amount *help
¥31,000,000 (Direct Cost : ¥31,000,000)
Fiscal Year 2005 : ¥8,000,000 (Direct Cost : ¥8,000,000)
Fiscal Year 2004 : ¥8,000,000 (Direct Cost : ¥8,000,000)
Fiscal Year 2003 : ¥7,500,000 (Direct Cost : ¥7,500,000)
Fiscal Year 2002 : ¥7,500,000 (Direct Cost : ¥7,500,000)
Synthesis, Structure, and Reactivity of a Stable Zerovalent Ruthenium Aqua Complex
Water is one of the most abundant substances in biological systems, where it acts as a solvent, reagent and architectural component. Although a water molecule has C_<2v> symmetry and is itself achiral, the oxygen atom of water can become a chiral center by coordination to a Lewis acid (transition metal) and by hydrogen bonding. However, there have no previously reported experimental evidences and concepts. We report the first synthesis and structure of an artificial model complex containing 'chiral water', Ru(dppe)(dmfm)_2(H_2O) (1) [dppe=1,2-bis(diphenylphosphino)ethane, dmfm=dimethyl fumarate] by reacting H_2O with Ru(η^6-cot)(dmfm)_2 (2) [cot=1,3,5-cyclooctatriene] and dppe. The dynamic behaviors of 1 in solution based on variable-temperature 1H NMR, line-shape analysis of the spectra, and DFT calculation are also disclosed.
Formation of Binuclear Ru(II) Aqua Complexes Bearing P-P-O Facial Tridentate Ligands and Oxametallacycle Moieties
The reaction of racemic Ru(η^6-cot)(dmfm)_2 (2) with water in the presence of either (S,S)-DIPAMP or o-MeO-dppe afforded unique binuclear Ru(II) aqua complexes 3, where two oxaruthenacycles are combined and hold a water molecule by coordination and two different hydrogen bonds. The molecular structures of 3 were revealed by X-ray crystallography.
Synthesis and Characterization of a Novel (μ3-Oxo)tetraruthenium Cluster
A novel (μ^3-oxo)tetraruthenium cluster (4) was synthesized in an isolate yield of 73% by the reaction of a zerovalent Ru(η^6-cot)(dmfm)2 (2) with water under reflux in 1,4-dioxane for 6 h. The X-ray structure of 4 as well as a possible formation mechanism has been disclosed.