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Water-Exchange Study Revealed Unexpected Substitution Behavior of [(CO)2(NO)Re(H2O)3]2+ in Aqueous Media.

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Title: Water-Exchange Study Revealed Unexpected Substitution Behavior of [(CO)2(NO)Re(H2O)3]2+ in Aqueous Media.
Authors: Lehaire, Marie-Line1,2, Grundler, Pascal V.2,3, Steinhauser, Stefan4, Marti, Niklaus1, Helm, Lothar3, Hegetschweiler, Kaspar4, Schibii, Roger roger.schibli@psi.ch, Merbach, André E.3 andre.merbach@epfl.ch
Source: Inorganic Chemistry. 5/15/2006, Vol. 45 Issue 10, p4199-4204. 6p. 1 Chart, 5 Graphs.
Subjects: Nuclear magnetic resonance, Hydrogen-ion concentration, Acidity function, Spectrum analysis, Physical & theoretical chemistry
Abstract: The pH-dependent water-exchange rates of [(CO)2(NO)Re(H2Ocis)2(H2Otrans)]2+ (1) in aqueous media were investigated by means of 170 NMR spectroscopy at 298 K. Because of the low pKa value found for 1 (pKa = 1.4 ± 0.3), the water-exchange rate constant kobsH2Otrans/cis was analyzed with a two-pathway model in which kReH2Otrans/cis and kReOHH2Otrans/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 kReOHH2Otrans and kReOHH2Ocis were determined as (4.2 ± 2) × 10-3 s-1 and (5.8 ± 2) × 10-4 s-1, respectively, kReH2Otrans and kReH2Ocis 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16O → C*O exchange was also observed via NMR and IR spectroscopy. It was found to proceed through 1 and 2, with rate constants kReCO and kReOHCO of (19 ± 4) × 10-3 s-1 and (4 ± 3) × 10-3 s-1, respectively. On the other hand, N16O → N*O exchange was not observed. [ABSTRACT FROM AUTHOR]
Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Water-Exchange Study Revealed Unexpected Substitution Behavior of [(CO)<subscript>2</subscript>(NO)Re(H<subscript>2</subscript>O)<subscript>3</subscript>]<superscript>2+</superscript> in Aqueous Media.
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  Data: <searchLink fieldCode="AR" term="%22Lehaire%2C+Marie-Line%22">Lehaire, Marie-Line</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Grundler%2C+Pascal+V%2E%22">Grundler, Pascal V.</searchLink><relatesTo>2,3</relatesTo><br /><searchLink fieldCode="AR" term="%22Steinhauser%2C+Stefan%22">Steinhauser, Stefan</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Marti%2C+Niklaus%22">Marti, Niklaus</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Helm%2C+Lothar%22">Helm, Lothar</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Hegetschweiler%2C+Kaspar%22">Hegetschweiler, Kaspar</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Schibii%2C+Roger%22">Schibii, Roger</searchLink><i> roger.schibli@psi.ch</i><br /><searchLink fieldCode="AR" term="%22Merbach%2C+André+E%2E%22">Merbach, André E.</searchLink><relatesTo>3</relatesTo><i> andre.merbach@epfl.ch</i>
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  Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 5/15/2006, Vol. 45 Issue 10, p4199-4204. 6p. 1 Chart, 5 Graphs.
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  Data: <searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance%22">Nuclear magnetic resonance</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen-ion+concentration%22">Hydrogen-ion concentration</searchLink><br /><searchLink fieldCode="DE" term="%22Acidity+function%22">Acidity function</searchLink><br /><searchLink fieldCode="DE" term="%22Spectrum+analysis%22">Spectrum analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Physical+%26+theoretical+chemistry%22">Physical & theoretical chemistry</searchLink>
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  Group: Ab
  Data: The pH-dependent water-exchange rates of [(CO)2(NO)Re(H2Ocis)2(H2Otrans)]2+ (1) in aqueous media were investigated by means of 170 NMR spectroscopy at 298 K. Because of the low pKa value found for 1 (pKa = 1.4 ± 0.3), the water-exchange rate constant kobsH2Otrans/cis was analyzed with a two-pathway model in which kReH2Otrans/cis and kReOHH2Otrans/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 kReOHH2Otrans and kReOHH2Ocis were determined as (4.2 ± 2) × 10-3 s-1 and (5.8 ± 2) × 10-4 s-1, respectively, kReH2Otrans and kReH2Ocis 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16O → C*O exchange was also observed via NMR and IR spectroscopy. It was found to proceed through 1 and 2, with rate constants kReCO and kReOHCO of (19 ± 4) × 10-3 s-1 and (4 ± 3) × 10-3 s-1, respectively. On the other hand, N16O → N*O exchange was not observed. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – SubjectFull: Acidity function
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      – SubjectFull: Spectrum analysis
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              Text: 5/15/2006
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