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Mechanistic Changeover for the Water Substition on fac-[(CO)3Re(H2O)3]+ Revealed by High-Pressure NMR.

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Title: Mechanistic Changeover for the Water Substition on fac-[(CO)3Re(H2O)3]+ Revealed by High-Pressure NMR.
Authors: Grundler, Pascal V.1, Salignac, Bernadette1, Cayemittes, Sonia1, Alberto, Roger2, Merbach, André E.1 Andre.Merbach@epfl.ch
Source: Inorganic Chemistry. 2/9/2004, Vol. 43 Issue 3, p865-873. 9p.
Subjects: Substitution reactions, Ligands (Chemistry), Nuclear magnetic resonance, Water, Scission (Chemistry), Dimethyl sulfide, Carbon compounds, Metal complexes
Abstract: The complex formation in water between the stable tricarbonyltriaqua fac-[(CO) 3Re(H 2O) 3]+ (1) complex and N- and S-donor ligands has been studied by high-pressure 1H NMR. Rate and equilibrium constants for the formation of [(CO)3Re(Pyz)(H2O)2]+, [(CO)3(H2O)2Re(μ-Pyz)Re(H2O)2(CO)3]²+, [(CO)3Re(THT)(H2O)2]+, and [(CO)3Re(DMS)n(H2O)3-n]+ (n = 1−3) (Pyz = pyrazine, THT = tetrahydrothiophene, DMS = dimethyl sulfide) have been determined and are in accord with previous results (Salignac, B.; Grundler, P. V.; Cayemittes, S.; Frey, U.; Scopelliti, R.; Merbach, A. E.; Hedinger, R.; Hegetschweiler, K.; Alberto, R.; Prinz, U.; Raabe, G.; Kölle, U.; Hall, S. Inorg. Chem. 2003, 42, 3516). The calculated interchange rate constant k′i (Eigen­;Wilkins mechanism) increases from the hard O- and N-donors to the soft S-donors, as exemplified by the following series: TFA (trifluoroacetate) (k′i = 2.9 × 10−³ S−¹) < Br- < CH3CN < Pyz < THT < DMS < TU (thiourea) (k′i= 41.5 × 10−³ s−¹). On the other hand, k′i values remain close to that of water exchange kex on 1 (kex = 6.3 × 10−³ S−¹). Thus, an Id mechanism was assigned, suggesting however the possibility of a slight deviation toward an associatively activated mechanism with the S-donor ligands. Activation volumes determined by high-pressure NMR, for Pyz as ΔV≠f,1 = +5.4 ± 1.5, ΔV≠r,1 = +7.9 ± 1.2 cm3 mol−¹, for THT as ΔV≠f,1 = −6.6 ± 1, ΔV≠r,1 = −6.2 ± 1 cm3 mo1−¹, and for DMS as ΔV≠f,1 = −12 ± 1, ΔV≠r,1 = −10 ± 2 cm3 mol−¹ revealed the ambivalent character of 1 toward water substitution. Hence, these findings are interpreted as a gradual changeover of the reaction mechanism from a dissociatively activated one (Id), with the hard O- and N-donor ligands, to an associatively activated one (la), with the soft S-donor ligands. [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: Mechanistic Changeover for the Water Substition on fac-[(CO)&lt;subscript&gt;3&lt;/subscript&gt;Re(H&lt;subscript&gt;2&lt;/subscript&gt;O)&lt;subscript&gt;3&lt;/subscript&gt;]&lt;superscript&gt;+&lt;/superscript&gt; Revealed by High-Pressure NMR.
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  Data: &lt;searchLink fieldCode=&quot;JN&quot; term=&quot;%22Inorganic+Chemistry%22&quot;&gt;Inorganic Chemistry&lt;/searchLink&gt;. 2/9/2004, Vol. 43 Issue 3, p865-873. 9p.
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  Data: The complex formation in water between the stable tricarbonyltriaqua fac-[(CO) 3Re(H 2O) 3]+ (1) complex and N- and S-donor ligands has been studied by high-pressure 1H NMR. Rate and equilibrium constants for the formation of [(CO)3Re(Pyz)(H2O)2]+, [(CO)3(H2O)2Re(μ-Pyz)Re(H2O)2(CO)3]&#178;+, [(CO)3Re(THT)(H2O)2]+, and [(CO)3Re(DMS)n(H2O)3-n]+ (n = 1−3) (Pyz = pyrazine, THT = tetrahydrothiophene, DMS = dimethyl sulfide) have been determined and are in accord with previous results (Salignac, B.; Grundler, P. V.; Cayemittes, S.; Frey, U.; Scopelliti, R.; Merbach, A. E.; Hedinger, R.; Hegetschweiler, K.; Alberto, R.; Prinz, U.; Raabe, G.; K&#246;lle, U.; Hall, S. Inorg. Chem. 2003, 42, 3516). The calculated interchange rate constant k′i (Eigen&#173;;Wilkins mechanism) increases from the hard O- and N-donors to the soft S-donors, as exemplified by the following series: TFA (trifluoroacetate) (k′i = 2.9 &#215; 10−&#179; S−&#185;) &lt; Br- &lt; CH3CN &lt; Pyz &lt; THT &lt; DMS &lt; TU (thiourea) (k′i= 41.5 &#215; 10−&#179; s−&#185;). On the other hand, k′i values remain close to that of water exchange kex on 1 (kex = 6.3 &#215; 10−&#179; S−&#185;). Thus, an Id mechanism was assigned, suggesting however the possibility of a slight deviation toward an associatively activated mechanism with the S-donor ligands. Activation volumes determined by high-pressure NMR, for Pyz as ΔV≠f,1 = +5.4 &#177; 1.5, ΔV≠r,1 = +7.9 &#177; 1.2 cm3 mol−&#185;, for THT as ΔV≠f,1 = −6.6 &#177; 1, ΔV≠r,1 = −6.2 &#177; 1 cm3 mo1−&#185;, and for DMS as ΔV≠f,1 = −12 &#177; 1, ΔV≠r,1 = −10 &#177; 2 cm3 mol−&#185; revealed the ambivalent character of 1 toward water substitution. Hence, these findings are interpreted as a gradual changeover of the reaction mechanism from a dissociatively activated one (Id), with the hard O- and N-donor ligands, to an associatively activated one (la), with the soft S-donor ligands. [ABSTRACT FROM AUTHOR]
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  Data: &lt;i&gt;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&#39;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.&lt;/i&gt; (Copyright applies to all Abstracts.)
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        Value: 10.1021/ic034969a
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      – Code: eng
        Text: English
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        PageCount: 9
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    Subjects:
      – SubjectFull: Substitution reactions
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Nuclear magnetic resonance
        Type: general
      – SubjectFull: Water
        Type: general
      – SubjectFull: Scission (Chemistry)
        Type: general
      – SubjectFull: Dimethyl sulfide
        Type: general
      – SubjectFull: Carbon compounds
        Type: general
      – SubjectFull: Metal complexes
        Type: general
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      – TitleFull: Mechanistic Changeover for the Water Substition on fac-[(CO)3Re(H2O)3]+ Revealed by High-Pressure NMR.
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            NameFull: Grundler, Pascal V.
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            NameFull: Salignac, Bernadette
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            NameFull: Cayemittes, Sonia
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            NameFull: Alberto, Roger
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              M: 02
              Text: 2/9/2004
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              Y: 2004
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              Value: 43
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