Abstract
The newly synthesized mer-trans-[RuCl2(OH2)(PTA)3] (1) is the first compound isolated in solid state containing the Ru(PTA)3-fragment (PTA=1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane). Dissolution of 1 in aqueous HCl leads to mer-[RuCl3(HPTA)3]Cl2 (2) which is stable in the dark but is transformed into fac-[RuCl3(HPTA)3]Cl2 (3) under visible light. Irradiation with visible light of an aqueous solution of 1 at room temperature or refluxing of the same solution in the dark leads to the formation of [{Ru(PTA)3}2(μ-Cl)3]Cl (4). The dinuclear complex 4 was also formed upon irradiation of solutions of PTA and various Ru(II)-complexes ([RuCl2(DMSO)4], [{RuCl2(η6-p-cymene)}2]) or cis-cis-trans-[RuCl2(DMSO)2(PTA)2]). All complexes were characterized by elemental analysis and NMR spectroscopy, furthermore solid state structures of 2·1.25H2O, 3·HCl·2H2O and 4·9H2O were also determined by single crystal X-ray diffraction. We have investigated the influence of the above photochemical processes on reduction of benzaldehyde and cinnamaldehyde with trans-[RuCl2(PTA)4] and cis-cis-trans-[RuCl2(DMSO)2L2] (L=PTA, (PTA-Me)CF3SO3, (PTA-Bn)Cl; Me=methyl, Bn=benzyl) complexes as catalysts. The effect of visible light on benzonitrile hydration with various Ru(II)-PTA catalysts is also reported.
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