title: Water-exchange study revealed unexpected substitution behavior of [(CO)2(NO)Re(H2O)3]2+ in aqueous media.
abstract: The pH-dependent water-exchange rates of [(CO)2(NO)Re(H2O(cis))2(H2O(trans))]2+ (1) in aqueous media were investigated by means of 17O NMR spectroscopy at 298 K. Because of the low pK(a) value found for 1 (pK(a) = 1.4 +/- 0.3), the water-exchange rate constant k(obs)(H2O(trans/cis)) was analyzed with a two-pathway model in which k(Re)(H2O(trans/cis)) and k(ReOH)(H2O)(trans/cis)) denote the water-exchange rate constants in trans or cis position to the nitrosyl ligand on 1 and on the monohydroxo species [(CO)2(NO)Re(H2O)2(OH)]+ (2), respectively. Whereas the rate constants k(ReOH)(H2O)(trans)) and k(ReOH)(H2O)(cis)) were determined as (4.2 +/- 2) x 10(-3) s(-1) and (5.8 +/- 2) x 10(-4) s(-1), respectively, k(Re)(H2O)(trans)) and k(Re)(H2O)(cis)) were too small to be determined in the presence of the much more reactive species 2. Apart from the water exchange, an unexpectedly fast C identical with 16O --> C identical withO exchange was also observed via NMR and IR spectroscopy. It was found to proceed through 1 and 2, with rate constants k(Re)(CO) and k(ReOH)(CO) of (19 +/- 4) x 10(-3) s(-1) and (4 +/- 3) x 10(-3) s(-1), respectively. On the other hand, N identical with 16O --> N identical with *O exchange was not observed.
authors: Center for Radiopharmaceutical Science, ETH-PSI-USZ, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland.
authors: Marie-Line
authors: ML
authors: Lehaire
authors: Pascal V
authors: PV
authors: Grundler
authors: Stefan
authors: S
authors: Steinhauser
authors: Niklaus
authors: N
authors: Marti
authors: Lothar
authors: L
authors: Helm
authors: Kaspar
authors: K
authors: Hegetschweiler
authors: Roger
authors: R
authors: Schibli
authors: André E
authors: AE
authors: Merbach