The base hydrolysis of [Rh(tren)Cl,]+ generates fi-[Rh(tren)ClOH]+ identical with the photochemical product, while earlier work shows that aquation of [Rh(tren)CI,]+ in acidic solution gives the a isomer. The kinetics of the hydrolysis of [Rh(tren)Cl,]+ and a-and fi-[Rh(tren)ClOH]+ in alkaline solution have been investigated, as have the kinetics of the acid hydrolysis of fi-[Rh(tren)Cl(H20)]2+. The hydrolyses of the dichloro and achlorohydroxo ions (k, and k2) are accelerated by hydroxide, whereas the rate of hydrolysis of the fi isomer (k,) is only marginally affected by the presence of hydroxide. In acidic solution in the presence of excess CI-, [Rh(tren)(OH2)2]3+ undergoes two distinct chloride anation steps (k, and k5). Kinetic data were collected on the following reactions: [Rh(tren)Cl,]' P-[Rh(tren)ClOH]-0 Hk OH--1 k, CT [ Rh(tren)Cl(OH)] + -0' ;;t [ Rh (tr en)(OH) ,I + [Rh(tren)(OH,),] 3+-?-B-[Rh(t~en)C10H,1 4 [Rh(tren)Cl,]' k k c1-c1-Reaction products were characterized in solution by electronic spectra and chemical analyses. The stereospecific substitutions and differences in substitution rates, for both the hydrolyses and anations, are explained in terms of different environments of the two nonamine coordination sites in [Rh(tren)XY]"+ complexes. The base hydrolysis and chloride anation data have been used in the synthesis of some new Rh(II1)-tren complexes. These have been isolated as solids and characterized by elemental analysis and visible and ultraviolet spectra.
IntroductionIn recent studies,2J the thermal and photochemical reactions of [Rh(tren)C12]+ (tren = P,fl,P"-triaminotriethylamine) were
Der Titelkomplex (I) erleidet sowohl bei der Säure‐katalysierten Aquotisierung als auch bei der Basen‐katalysierten Hydrolyse als auch bei der photoinduzierten Aquotisierung einen Fluoridverlust.
Das Titelkation (I) liefert bei Hydrolyse in verdünnt saurer Lösung zunächst den Komplex (II), bei dem eine Aminogruppe des vierzähnigen Aminliganden protoniert ist, der dann beim Erhitzen stufenweise über (III) in (IV) übergeht.
Die Kinetik der Hydrolyse von [RhC12(tren)] und von α‐ und β‐[RhC1(OH)(tren) 1" in alkalischer Lösung, die der sauren Hydrolyse von β‐[RhCl(tren)(OH,)] 2 und die der zweistufigen Chlorid‐Anation von [Rh(tren)(OH2)2] 3+ in saurer Lösung wird untersucht.
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