Preparation and crystal structure of [Ru2(μ-Cl)3(P(CH2OH)3)6]Cl

Synthesis and catalytic activity of new, water-soluble mono- and dinuclear ruthenium(II) complexes containing 1,3,5-triaza-7-phosphaadamantane: Study of the effect of the visible light

“…[41] With P(Bu) 3 and P(CH 2 OH 3 ) 3 the dimerization took place even at room temperature, albeit in slow processes. [42][43][44] We have found that [{Ru(PTA) 3 } 2 (μ-Cl can be also detected [26,27] .…”

“…PTA is stable in the dark. [23] However, upon irradiation (process ii) on Scheme 6), the solution turns green, and after addition of 1 eq PTA it becomes lemon yellow; the 31 P{ 1 H} NMR spectrum In comparison, although cis-cis-trans-[RuCl 2 (DMSO) 2 (PTA-Me) 2 ](CF 3 SO 3 ) 2 is also lightsensitive, irradiation by visible light in the presence of 1 eq (PTA-Me)(CF 3 SO 3 ) yields the known [40] trans-[RuCl In contrast to the analogous water-soluble dinuclear complex containing P(CH 2 OH 3 ) 3 , [44] compound 4 is air-stable both in solution and in solid form. Single crystals of 4•9H 2 O were obtained by layering 2-propanol on an aqueous solution of the complex.…”

“…Finally, 4 is constituted by two {Ru(PTA) 3 } units linked through the metals by three bridging Cl -; the metal atoms are coordinated in a distorted octahedral geometry to three PTA ligands through the P atoms. According to the Cambridge Structural Database [45] to date only 8 chloro-bridged dinuclear Ru(II)-complexes with monodentate phosphine ligands (similar to 4) have been characterized in solid state [42][43][44][46][47][48][49] . The distances Ru-P and Ru-Cl for the two metals are not the same (Ru1-P1 = 2.2672( 9 Cl) 3 Ru{P(CH 3 ) 3 } 3 ]X (X=BF 4 [46] , Cl [47] ) both ruthenium atoms have equal distances to phosphines as well as to chlorides; in the chloride salt the average Ru-P distance (2.266(2) Å) was found larger while the average Ru-Cl distance (2.503(6) Å) almost the same as in 4.…”

“…Since already such a small excess of chloride is sufficient to prevent aquation [26,27] hydrido-complexes, such as those identified in ref. [44] ). These results lend further credit to earlier investigations on such catalytic systems with no exclusion of light and suggest that photoactivity of [RuCl x (OH 2 ) y (PTA) 6-x-y ] catalysts is more likely to influence reactions (such as hydrogenation or redox isomerization) in the absence of a high concentrations of other coordinating ligands such as, for example, HCOO -.…”