Aqueous Organometallic Chemistry. Synthesis and Solution Equilibria of Trisodium Carbonylchlorotris[3-(diphenylphosphino-κP)benzenesulfonato]hydridoruthenate(3−) ([RuH(Cl)(CO){m-(Ph2P)C6H4SO3Na}3]) and Trisodium Aquacarbonyltris[3-(diphenylphosphino-κP)benzenesulfonato]hydridoruthenate(2−) Tetrafluoroborate(1−) ([RuH(CO)(H2O){m-(Ph2P)C6H4SO3Na}3] [BF4])

✍ Scribed by Gábor Papp; Henrietta Horváth; Ágnes Kathó; Ferenc Joó

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: German
• Weight: 98 KB
• Volume: 88
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200590039

✦ Synopsis

Abstract

An improved procedure for the preparation of the known H~2~O‐soluble hydrogenation and hydroformylation catalyst, [RuH(Cl)(CO)(__m__tppms)~3~] (__m__tppms=meta‐monosulfonated triphenylphosphine) was developed. In contrast to the methods reported earlier, this synthesis yields the complex free of __m__tppms impurities. ^1^H‐ and ^31^P{H}‐NMR measurements revealed that in aqueous solution, [RuH(Cl)(CO)(__m__tppms)~3~] reversibly dissociated to give [RuH(CO)(H~2~O)(__m__tppms)~3~]^+^ (Scheme). The equilibrium constant of this dissociation was determined as 9.8⋅10^−2^ M at 293 K. Such a dissociation was not observed in MeOH but took place to varying degrees in MeOH/H~2~O mixtures of varying composition. [RuH(CO)(H~2~O)(__m__tppms)~3~][BF~4~] was also obtained on an independent synthetic route: by ligand exchange in [RuH(CO)(NCMe)~2~(PPh~3~)~2~][BF~4~] (Scheme). The results may help the understanding of the mechanisms of reactions catalyzed by [RuH(Cl)(CO)(__m__tppms)~3~] in aqueous solutions or in aqueous–organic biphasic systems.