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Protonolysis of Platinum(II) and Palladium(II) Methyl Complexes: A Combined Experimental and Theoretical Investigation.

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Title: Protonolysis of Platinum(II) and Palladium(II) Methyl Complexes: A Combined Experimental and Theoretical Investigation.
Authors: John E. Bercaw1, George S. Chen1, Jay A. Labinger1, Bo-Lin Lin1
Source: Organometallics. Oct2010, Vol. 29 Issue 19, p4354-4359. 6p.
Subjects: Organoplatinum compounds, Organopalladium compounds, Complex compounds, Density functionals, Temperature effect, Quantum tunneling, Electron donor-acceptor complexes, Ligands (Chemistry)
Abstract: The protonolysis of platinum(II) and palladium(II) methyl complexes has been investigated by both experiment and computation. Previously the protonolysis of (COD)PtII(CH3)2by CF3COOY or (dppe)PdII(CH3)2by CF3CY2OY (Y = H, D) was found to be accompanied by abnormally large and highly temperature-dependent kinetic isotope effects (KIEs), suggesting the involvement of tunneling. Here we find normal KIEs and no evidence of tunneling for protonolysis of (tmeda)PtII(CH3)Cl by CF3COOY (Y = H, D). Density functional theory (DFT) calculations indicate that protonation at the metal center followed by reductive coupling to the methane σ adduct (stepwise pathway) is favored for Pt complexes with good electron donor ligands, whereas direct protonation of the M−CH3bond to generate the methane σ adduct (concerted pathway) is favored for Pt with electron-withdrawing ligands as well as for Pd. We suggest that KIE behavior consistent with tunneling may be an experimental indicator of the concerted pathway. [ABSTRACT FROM AUTHOR]
Copyright of Organometallics 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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DbLabel: Engineering Source
An: 54319916
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  Data: Protonolysis of Platinum(II) and Palladium(II) Methyl Complexes: A Combined Experimental and Theoretical Investigation.
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  Data: <searchLink fieldCode="JN" term="%22Organometallics%22">Organometallics</searchLink>. Oct2010, Vol. 29 Issue 19, p4354-4359. 6p.
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  Data: <searchLink fieldCode="DE" term="%22Organoplatinum+compounds%22">Organoplatinum compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Organopalladium+compounds%22">Organopalladium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Complex+compounds%22">Complex compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink><br /><searchLink fieldCode="DE" term="%22Temperature+effect%22">Temperature effect</searchLink><br /><searchLink fieldCode="DE" term="%22Quantum+tunneling%22">Quantum tunneling</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+donor-acceptor+complexes%22">Electron donor-acceptor complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink>
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  Data: The protonolysis of platinum(II) and palladium(II) methyl complexes has been investigated by both experiment and computation. Previously the protonolysis of (COD)PtII(CH3)2by CF3COOY or (dppe)PdII(CH3)2by CF3CY2OY (Y = H, D) was found to be accompanied by abnormally large and highly temperature-dependent kinetic isotope effects (KIEs), suggesting the involvement of tunneling. Here we find normal KIEs and no evidence of tunneling for protonolysis of (tmeda)PtII(CH3)Cl by CF3COOY (Y = H, D). Density functional theory (DFT) calculations indicate that protonation at the metal center followed by reductive coupling to the methane σ adduct (stepwise pathway) is favored for Pt complexes with good electron donor ligands, whereas direct protonation of the M−CH3bond to generate the methane σ adduct (concerted pathway) is favored for Pt with electron-withdrawing ligands as well as for Pd. We suggest that KIE behavior consistent with tunneling may be an experimental indicator of the concerted pathway. [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Organometallics 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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        Value: 10.1021/om100655w
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        Text: English
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        Type: general
      – SubjectFull: Organopalladium compounds
        Type: general
      – SubjectFull: Complex compounds
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      – SubjectFull: Density functionals
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      – SubjectFull: Quantum tunneling
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      – SubjectFull: Electron donor-acceptor complexes
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      – SubjectFull: Ligands (Chemistry)
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      – TitleFull: Protonolysis of Platinum(II) and Palladium(II) Methyl Complexes: A Combined Experimental and Theoretical Investigation.
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              Text: Oct2010
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              Y: 2010
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