Reactivity of the Organometallic fac-[(CO)[sub 3]Re[sup I](H[sub 2]O)[sub 3]][sup +] Aquaion. Kinetic and Thermodynamic Properties of H[sub 2]O Substitution.
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| Title: | Reactivity of the Organometallic fac-[(CO)[sub 3]Re[sup I](H[sub 2]O)[sub 3]][sup +] Aquaion. Kinetic and Thermodynamic Properties of H[sub 2]O Substitution. |
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| Authors: | Salignac, Bernadette, Grundler, Pascal V., Cayemittes, Sonia, Frey, Urban, Scopelliti, Rosario, Merbach, André E., Hedinger, Roman, Hegetschweller, Kaspar, Alberto, Roger, Prinz, Ulrich, Reabe, Gerhard, Kölle, Ulrich, Hall, Syd |
| Source: | Inorganic Chemistry. 6/2/2003, Vol. 42 Issue 11, p3516. 11p. 4 Diagrams, 6 Charts, 5 Graphs. |
| Subjects: | Organometallic compounds, Water chemistry |
| Abstract: | The water exchange process on [(CO)[sub 3]Re(H[sub 2]O)[sub 3]][sup +] (1) was kinetically investigated by [sup 17]O NMR. The acidity dependence of the observed rate constant kobs was analyzed with a two pathways model in which k[sub ex] (k[sub ex][sup 298] = (6.3 ± 0.1 × 10[sup -3] S[sup -1]) and k[sub OH] (k[sub OH][sup 298] = 27 ± 1 s[sup -1]) denote the water exchange rate constants on 1 and on the monohydroxo species [(CO)[sub 3]Re¹(H[sub 2]O)[sub 2](OH)], respectively. The kinetic contribution of the basic form was proved to be significant only at [H[sup +]] < 3 × 10[sup -3] M. Above this limiting [H[sup +]] concentration, kinetic investigations can be unambiguously conducted on the triaqua cation (1). The variable temperature study has led to the determination of the activation parameters ΔH[sup ‡][sub ex] = 90 ± 3 kJ mol[sup -1], ΔS[sup ‡][sub ex] = +14 ± 10 J K [sup -1] mol[sup -l], the latter being indicative of a dissociative activation mode for the water exchange process. To support this assumption, water substitution reaction on 1 has been followed by [sup 17]O/¹H/[sup 13]C/[sup 19]F NMR with ligands of various nucleophilicities (TFA, Br[sup -], CH[sub 3]CN, Hbipy[sup +], Hphen[sup +], DMS, TU). With unidentate ligands, except Br[sup -], the mono-, bi-, and tricomplexes were formed by water substitution. With bidentate ligands, bipy and phen, the chelate complexes [(CO)[sub 3]Re(H[sub 2]O)(bipy)]CF[sub 3]SO[sub 3] (2) and [(CO)[sub 3]Re(H[sub 2]O)(phen)](NO[sub 3])[sub 0.5](CF[sub 3]SO[sub 3])[sub 0.5]·H[sub 2]O (3) were isolated and X-ray characterized. For each ligand, the calculated interchange rate constants K[sub i] (2.9 × 10[sup -3] (TFA) < K[sub 1] < 41.5 × 10[sup -3] (TU) s[sup -1]) were found in the same order as the water exchange rate constant k[sub ex], the S-donor ligands being slightly more reactive. This result is indicative of Id mechanism... [ABSTRACT FROM AUTHOR] |
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| Items | – Name: Title Label: Title Group: Ti Data: Reactivity of the Organometallic fac-[(CO)[sub 3]Re[sup I](H[sub 2]O)[sub 3]][sup +] Aquaion. Kinetic and Thermodynamic Properties of H[sub 2]O Substitution. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Salignac%2C+Bernadette%22">Salignac, Bernadette</searchLink><br /><searchLink fieldCode="AR" term="%22Grundler%2C+Pascal+V%2E%22">Grundler, Pascal V.</searchLink><br /><searchLink fieldCode="AR" term="%22Cayemittes%2C+Sonia%22">Cayemittes, Sonia</searchLink><br /><searchLink fieldCode="AR" term="%22Frey%2C+Urban%22">Frey, Urban</searchLink><br /><searchLink fieldCode="AR" term="%22Scopelliti%2C+Rosario%22">Scopelliti, Rosario</searchLink><br /><searchLink fieldCode="AR" term="%22Merbach%2C+André+E%2E%22">Merbach, André E.</searchLink><br /><searchLink fieldCode="AR" term="%22Hedinger%2C+Roman%22">Hedinger, Roman</searchLink><br /><searchLink fieldCode="AR" term="%22Hegetschweller%2C+Kaspar%22">Hegetschweller, Kaspar</searchLink><br /><searchLink fieldCode="AR" term="%22Alberto%2C+Roger%22">Alberto, Roger</searchLink><br /><searchLink fieldCode="AR" term="%22Prinz%2C+Ulrich%22">Prinz, Ulrich</searchLink><br /><searchLink fieldCode="AR" term="%22Reabe%2C+Gerhard%22">Reabe, Gerhard</searchLink><br /><searchLink fieldCode="AR" term="%22Kölle%2C+Ulrich%22">Kölle, Ulrich</searchLink><br /><searchLink fieldCode="AR" term="%22Hall%2C+Syd%22">Hall, Syd</searchLink> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 6/2/2003, Vol. 42 Issue 11, p3516. 11p. 4 Diagrams, 6 Charts, 5 Graphs. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Organometallic+compounds%22">Organometallic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Water+chemistry%22">Water chemistry</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The water exchange process on [(CO)[sub 3]Re(H[sub 2]O)[sub 3]][sup +] (1) was kinetically investigated by [sup 17]O NMR. The acidity dependence of the observed rate constant kobs was analyzed with a two pathways model in which k[sub ex] (k[sub ex][sup 298] = (6.3 ± 0.1 × 10[sup -3] S[sup -1]) and k[sub OH] (k[sub OH][sup 298] = 27 ± 1 s[sup -1]) denote the water exchange rate constants on 1 and on the monohydroxo species [(CO)[sub 3]Re¹(H[sub 2]O)[sub 2](OH)], respectively. The kinetic contribution of the basic form was proved to be significant only at [H[sup +]] < 3 × 10[sup -3] M. Above this limiting [H[sup +]] concentration, kinetic investigations can be unambiguously conducted on the triaqua cation (1). The variable temperature study has led to the determination of the activation parameters ΔH[sup ‡][sub ex] = 90 ± 3 kJ mol[sup -1], ΔS[sup ‡][sub ex] = +14 ± 10 J K [sup -1] mol[sup -l], the latter being indicative of a dissociative activation mode for the water exchange process. To support this assumption, water substitution reaction on 1 has been followed by [sup 17]O/¹H/[sup 13]C/[sup 19]F NMR with ligands of various nucleophilicities (TFA, Br[sup -], CH[sub 3]CN, Hbipy[sup +], Hphen[sup +], DMS, TU). With unidentate ligands, except Br[sup -], the mono-, bi-, and tricomplexes were formed by water substitution. With bidentate ligands, bipy and phen, the chelate complexes [(CO)[sub 3]Re(H[sub 2]O)(bipy)]CF[sub 3]SO[sub 3] (2) and [(CO)[sub 3]Re(H[sub 2]O)(phen)](NO[sub 3])[sub 0.5](CF[sub 3]SO[sub 3])[sub 0.5]·H[sub 2]O (3) were isolated and X-ray characterized. For each ligand, the calculated interchange rate constants K[sub i] (2.9 × 10[sup -3] (TFA) < K[sub 1] < 41.5 × 10[sup -3] (TU) s[sup -1]) were found in the same order as the water exchange rate constant k[sub ex], the S-donor ligands being slightly more reactive. This result is indicative of Id mechanism... [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab 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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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ic0341744 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 11 StartPage: 3516 Subjects: – SubjectFull: Organometallic compounds Type: general – SubjectFull: Water chemistry Type: general Titles: – TitleFull: Reactivity of the Organometallic fac-[(CO)[sub 3]Re[sup I](H[sub 2]O)[sub 3]][sup +] Aquaion. Kinetic and Thermodynamic Properties of H[sub 2]O Substitution. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Salignac, Bernadette – PersonEntity: Name: NameFull: Grundler, Pascal V. – PersonEntity: Name: NameFull: Cayemittes, Sonia – PersonEntity: Name: NameFull: Frey, Urban – PersonEntity: Name: NameFull: Scopelliti, Rosario – PersonEntity: Name: NameFull: Merbach, André E. – PersonEntity: Name: NameFull: Hedinger, Roman – PersonEntity: Name: NameFull: Hegetschweller, Kaspar – PersonEntity: Name: NameFull: Alberto, Roger – PersonEntity: Name: NameFull: Prinz, Ulrich – PersonEntity: Name: NameFull: Reabe, Gerhard – PersonEntity: Name: NameFull: Kölle, Ulrich – PersonEntity: Name: NameFull: Hall, Syd IsPartOfRelationships: – BibEntity: Dates: – D: 02 M: 06 Text: 6/2/2003 Type: published Y: 2003 Identifiers: – Type: issn-print Value: 00201669 Numbering: – Type: volume Value: 42 – Type: issue Value: 11 Titles: – TitleFull: Inorganic Chemistry Type: main |
| ResultId | 1 |
