Palladacycles with C,N-bidentate and N,C,N′-tridentate ligands: Structures, spectral study and catalytic methanolysis of Pdes
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| Title: | Palladacycles with C,N-bidentate and N,C,N′-tridentate ligands: Structures, spectral study and catalytic methanolysis of Pdes |
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| Authors: | Lu, Zhong-Lin1 luzl@bnu.edu.cn, Wang, Xue-Rui1, Liu, Bian-Bian1, Wang, Rui-Yao2 |
| Source: | Journal of Organometallic Chemistry. Sep2010, Vol. 695 Issue 19/20, p2191-2200. 10p. |
| Subjects: | Organopalladium compounds, Ligands (Chemistry), Molecular structure, Palladium catalysts, Nuclear magnetic resonance spectroscopy, Chemical kinetics, Pyridine, Pesticides |
| Abstract: | Abstract: Palladacycles 2–4 with C,N-bidentate and N,C,N′-tridentate ligands were prepared and characterized. The X-ray crystal structures of [2,6-bis(N,N-dimethylaminomethyl)phenyl-N,C1,N′-](aqua)palladium(II) triflate (2), (N,N-dimethylaminobenzyl-C1,N)(4-trifluoromethylpyridine)(aqua)palladium(II) triflate (3), and (N,N-dimethylaminobenzyl-C1,N)(4-N,N-dimethylaminopyridine)(aqua)palladium(II) triflate (4), were determined. While 2 is much less active, 3 and 4 effectively catalyze the methanolysis of the Pdes. The catalytic activities were higher with the trifluoromethylpyridine co-ligand as compared to palladacycles containing 4-N,N-dimethylaminopyridine and pyridine co-ligands. 1H NMR spectra and the catalytic kinetic dependences on concentration and pH revealed that the active species was a palladacycle containing one methoxide and one pyridine in the coordination sphere. A plot of the catalytic activity vs. free [pyridine] indicated the participation of a common species. The proposed catalytic mechanism involves a pre-equilibrium binding of the Pde to palladium(II) center followed by dissociation of the pyridine and subsequent cleavage of the P–OAr unit through the intramolecular displacement on phosphorus by the adjacent Pd-coordinated methoxide. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Organometallic Chemistry is the property of Elsevier B.V. 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.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 53053396 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Palladacycles with C,N-bidentate and N,C,N′-tridentate ligands: Structures, spectral study and catalytic methanolysis of Pdes – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Lu%2C+Zhong-Lin%22">Lu, Zhong-Lin</searchLink><relatesTo>1</relatesTo><i> luzl@bnu.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Wang%2C+Xue-Rui%22">Wang, Xue-Rui</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Liu%2C+Bian-Bian%22">Liu, Bian-Bian</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Wang%2C+Rui-Yao%22">Wang, Rui-Yao</searchLink><relatesTo>2</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Organometallic+Chemistry%22">Journal of Organometallic Chemistry</searchLink>. Sep2010, Vol. 695 Issue 19/20, p2191-2200. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Organopalladium+compounds%22">Organopalladium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Palladium+catalysts%22">Palladium catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance+spectroscopy%22">Nuclear magnetic resonance spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+kinetics%22">Chemical kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Pyridine%22">Pyridine</searchLink><br /><searchLink fieldCode="DE" term="%22Pesticides%22">Pesticides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Abstract: Palladacycles 2–4 with C,N-bidentate and N,C,N′-tridentate ligands were prepared and characterized. The X-ray crystal structures of [2,6-bis(N,N-dimethylaminomethyl)phenyl-N,C1,N′-](aqua)palladium(II) triflate (2), (N,N-dimethylaminobenzyl-C1,N)(4-trifluoromethylpyridine)(aqua)palladium(II) triflate (3), and (N,N-dimethylaminobenzyl-C1,N)(4-N,N-dimethylaminopyridine)(aqua)palladium(II) triflate (4), were determined. While 2 is much less active, 3 and 4 effectively catalyze the methanolysis of the Pdes. The catalytic activities were higher with the trifluoromethylpyridine co-ligand as compared to palladacycles containing 4-N,N-dimethylaminopyridine and pyridine co-ligands. 1H NMR spectra and the catalytic kinetic dependences on concentration and pH revealed that the active species was a palladacycle containing one methoxide and one pyridine in the coordination sphere. A plot of the catalytic activity vs. free [pyridine] indicated the participation of a common species. The proposed catalytic mechanism involves a pre-equilibrium binding of the Pde to palladium(II) center followed by dissociation of the pyridine and subsequent cleavage of the P–OAr unit through the intramolecular displacement on phosphorus by the adjacent Pd-coordinated methoxide. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Organometallic Chemistry is the property of Elsevier B.V. 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: 10.1016/j.jorganchem.2010.06.002 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 2191 Subjects: – SubjectFull: Organopalladium compounds Type: general – SubjectFull: Ligands (Chemistry) Type: general – SubjectFull: Molecular structure Type: general – SubjectFull: Palladium catalysts Type: general – SubjectFull: Nuclear magnetic resonance spectroscopy Type: general – SubjectFull: Chemical kinetics Type: general – SubjectFull: Pyridine Type: general – SubjectFull: Pesticides Type: general Titles: – TitleFull: Palladacycles with C,N-bidentate and N,C,N′-tridentate ligands: Structures, spectral study and catalytic methanolysis of Pdes Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Lu, Zhong-Lin – PersonEntity: Name: NameFull: Wang, Xue-Rui – PersonEntity: Name: NameFull: Liu, Bian-Bian – PersonEntity: Name: NameFull: Wang, Rui-Yao IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 09 Text: Sep2010 Type: published Y: 2010 Identifiers: – Type: issn-print Value: 0022328X Numbering: – Type: volume Value: 695 – Type: issue Value: 19/20 Titles: – TitleFull: Journal of Organometallic Chemistry Type: main |
| ResultId | 1 |
