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Synthesis and structure of dichloropalladium(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2-organochalcogenomethylpyridine motif, and Mizoroki–Heck catalysis mediated by complexes of N,S-donor ligands

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Title: Synthesis and structure of dichloropalladium(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2-organochalcogenomethylpyridine motif, and Mizoroki–Heck catalysis mediated by complexes of N,S-donor ligands
Authors: Jones, Roderick C.1, Canty, Allan J.1 Allan.Canty@utas.edu.au, Gardiner, Michael G.1, Skelton, Brian W.2, Tolhurst, Vicki-Anne1, White, Allan H.2
Source: Inorganica Chimica Acta. Jan2010, Vol. 363 Issue 1, p77-87. 11p.
Subjects: Organopalladium compounds, Molecular structure, Complex compounds synthesis, Metal complexes, Ligands (Chemistry), Pyridine, Heck reaction, Catalysts
Abstract: Abstract: Ligands containing the 2-organochalcogenomethylpyridine motif with substituents in the 4- or 6-position of the pyridyl ring, R4,R6-pyCH2ER1 [R4 =R6 =H, ER1 =SMe (1), SeMe (2), SPh (6), SePh (7); R4 =Me, R6 =H, ER1 =SMe (3), SPh (8), SePh (9); R4 =H, R6 =Me, ER1 =SMe (4), SPh (10), SePh (11); R4 =H, R6 =Ph, ER1 =SMe (5), SPh (12), SePh (13)] are obtained on the reaction of R4,R6-pyMe with LiBu n followed by R1EER1. On reaction with PdCl2(NCMe)2, the ligands with a 6-phenyl substituent form cyclopalladated species PdCl{6-(o-C6H4)pyCH2ER1-C,N,E} (5a, 12a, 13a) with the structure of 13a (ER1 =SePh) confirmed by X-ray crystallography; other ligands form complexes of stoichiometry PdCl2(R4,R6-pyCH2ER1). Complexes with R6 =H are monomeric with N,E-bidentate configurations, confirmed by structural analysis for 3a (R4 =Me, ER1 =SMe), 7a (R4 =H, ER1 =SePh) and 9a (R4 =Me, ER1 =SePh). Two of the 6-methyl substituted complexes examined by X-ray crystallography are oligomeric with trans-PdCl2(N,E) motifs and bridging ligands, trimeric [PdCl2(μ-6-MepyCH2SPh-N,S)]3 (10a) and dimeric [PdCl2(μ-6-MepyCH2SePh-N,Se)] 2 (11a). This behaviour is attributed to avoidance of the Me···Cl interaction that would occur in the cis-bidentate configuration if the pyridyl plane had the same orientation with respect to the coordination plane as observed for 3a, 7a and 9a [dihedral angles 8.0(2)–16.8(2)°]. When examined as precatalysts for the Mizoroki–Heck reaction of n-butyl acrylate with aryl halides in N,N-dimethylacetamide at 120°C, the complexes exhibit the anticipated trends in yield (ArI>ArBr>ArCl, higher yield for electron withdrawing substituents in 4-RC6H4Br and 4-RC6H4Cl). The most active precatalysts are PdCl2(R4-pyCH2SMe-N,S) (R=H (1a), Me (3a)); complexes of the selenium containing ligands exhibit very low activity. For closely related ligands, the changes SMe to SPh, 6-H to 6-Me, and 6-H to 6-Ph lead to lower activity, consistent with involvement of both the pyridyl and chalcogen donors in reactions involving aryl bromides. The precatalyst PdCl2(pyCH2SMe-N,S) (1a) exhibits higher activity for the reaction of aryl chlorides in Bu n 4NCl at 120°C as a solvent under non-aqueous ionic liquid (NAIL) conditions. [Copyright &y& Elsevier]
Copyright of Inorganica Chimica Acta 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.)
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  Data: Synthesis and structure of dichloropalladium(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2-organochalcogenomethylpyridine motif, and Mizoroki–Heck catalysis mediated by complexes of N,S-donor ligands
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  Data: <searchLink fieldCode="AR" term="%22Jones%2C+Roderick+C%2E%22">Jones, Roderick C.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Canty%2C+Allan+J%2E%22">Canty, Allan J.</searchLink><relatesTo>1</relatesTo><i> Allan.Canty@utas.edu.au</i><br /><searchLink fieldCode="AR" term="%22Gardiner%2C+Michael+G%2E%22">Gardiner, Michael G.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Skelton%2C+Brian+W%2E%22">Skelton, Brian W.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Tolhurst%2C+Vicki-Anne%22">Tolhurst, Vicki-Anne</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22White%2C+Allan+H%2E%22">White, Allan H.</searchLink><relatesTo>2</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Inorganica+Chimica+Acta%22">Inorganica Chimica Acta</searchLink>. Jan2010, Vol. 363 Issue 1, p77-87. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Organopalladium+compounds%22">Organopalladium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Complex+compounds+synthesis%22">Complex compounds synthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Pyridine%22">Pyridine</searchLink><br /><searchLink fieldCode="DE" term="%22Heck+reaction%22">Heck reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink>
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  Data: Abstract: Ligands containing the 2-organochalcogenomethylpyridine motif with substituents in the 4- or 6-position of the pyridyl ring, R4,R6-pyCH2ER1 [R4 =R6 =H, ER1 =SMe (1), SeMe (2), SPh (6), SePh (7); R4 =Me, R6 =H, ER1 =SMe (3), SPh (8), SePh (9); R4 =H, R6 =Me, ER1 =SMe (4), SPh (10), SePh (11); R4 =H, R6 =Ph, ER1 =SMe (5), SPh (12), SePh (13)] are obtained on the reaction of R4,R6-pyMe with LiBu n followed by R1EER1. On reaction with PdCl2(NCMe)2, the ligands with a 6-phenyl substituent form cyclopalladated species PdCl{6-(o-C6H4)pyCH2ER1-C,N,E} (5a, 12a, 13a) with the structure of 13a (ER1 =SePh) confirmed by X-ray crystallography; other ligands form complexes of stoichiometry PdCl2(R4,R6-pyCH2ER1). Complexes with R6 =H are monomeric with N,E-bidentate configurations, confirmed by structural analysis for 3a (R4 =Me, ER1 =SMe), 7a (R4 =H, ER1 =SePh) and 9a (R4 =Me, ER1 =SePh). Two of the 6-methyl substituted complexes examined by X-ray crystallography are oligomeric with trans-PdCl2(N,E) motifs and bridging ligands, trimeric [PdCl2(μ-6-MepyCH2SPh-N,S)]3 (10a) and dimeric [PdCl2(μ-6-MepyCH2SePh-N,Se)] 2 (11a). This behaviour is attributed to avoidance of the Me···Cl interaction that would occur in the cis-bidentate configuration if the pyridyl plane had the same orientation with respect to the coordination plane as observed for 3a, 7a and 9a [dihedral angles 8.0(2)–16.8(2)°]. When examined as precatalysts for the Mizoroki–Heck reaction of n-butyl acrylate with aryl halides in N,N-dimethylacetamide at 120°C, the complexes exhibit the anticipated trends in yield (ArI>ArBr>ArCl, higher yield for electron withdrawing substituents in 4-RC6H4Br and 4-RC6H4Cl). The most active precatalysts are PdCl2(R4-pyCH2SMe-N,S) (R=H (1a), Me (3a)); complexes of the selenium containing ligands exhibit very low activity. For closely related ligands, the changes SMe to SPh, 6-H to 6-Me, and 6-H to 6-Ph lead to lower activity, consistent with involvement of both the pyridyl and chalcogen donors in reactions involving aryl bromides. The precatalyst PdCl2(pyCH2SMe-N,S) (1a) exhibits higher activity for the reaction of aryl chlorides in Bu n 4NCl at 120°C as a solvent under non-aqueous ionic liquid (NAIL) conditions. [Copyright &y& Elsevier]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Inorganica Chimica Acta 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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        Value: 10.1016/j.ica.2009.10.002
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      – Code: eng
        Text: English
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        PageCount: 11
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      – SubjectFull: Organopalladium compounds
        Type: general
      – SubjectFull: Molecular structure
        Type: general
      – SubjectFull: Complex compounds synthesis
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      – SubjectFull: Metal complexes
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      – SubjectFull: Ligands (Chemistry)
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      – SubjectFull: Pyridine
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      – SubjectFull: Heck reaction
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      – SubjectFull: Catalysts
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      – TitleFull: Synthesis and structure of dichloropalladium(II) complexes of heteroleptic N,S- and N,Se-donor ligands based on the 2-organochalcogenomethylpyridine motif, and Mizoroki–Heck catalysis mediated by complexes of N,S-donor ligands
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