New Rhodium(III) and Ruthenium(II) Water-Soluble Complexes with 3,5-Diaza-1-methyl-1-azonia7-phosphatricyclo[3.3.1.13,7]decane

The new water-soluble phosphine complexes of rhodium(lll), [Rhl4(mtpa)2]l (1), and ruthenium(ll), [Rul4(mtpa)2]• 2H20 (2) and [Rul2(mtpa)3(H20)]l3-2H20 (3) (mtpa = 3,5-diaza-1-methyl-1-azonia-7-phosphatricyclo[3.3.1.1 decane cation), have been prepared in the reactions of RhClsʹSIO and RuCIs-SIO in water in the presence of phosphine and potassium iodide. Properties and reactivity of the complexes have been investigated using H and P NMR and IR spectroscopies. The complexes have also been structurally characterized by single crystal X-ray diffraction studies. The compounds [Rhl4(mtpa)2]l and [Rul4(mtpa)2]*2H20 are zwitterionic octahedral complexes. The compounds were tested as catalysts for two-phase hydroformylation of 1-hexene and hydrogenation of cinnamaldehyde. Complex 1 is a selective catalyst for reduction of the C=C bond while complexes 2 and 3 selectively hydrogenate the C=O bond.