Complexes of late transition metals containing the mixed donor ligands 2,6-(RSCH2)2C5H3N (R = Ph, Me): Crystal structures of [{Cu(2,6-(PhSCH2)2C5H3N)(µ-X)}2] (X = Cl, Br) and [Ni(2,6-(PhSCH2)2C5H3N)Br2]

Ball, Rachel J.; Genge, Anthony R. J.; Radford, Alison L.; Skelton, Brian W.; Tolhurst, Vicki‐Anne; White, Allan H.

doi:10.1039/b104332n

Cited by 17 publications

(12 citation statements)

References 26 publications

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“…On the other hand, the analogue species with isobutyl substituents formed a dimer presenting two distorted octahedral nickel centers bridged by two chloride substituents resulting in the formula [NiCl{C 5 H 3 N‐2,6‐(CH 2 SR) 2 (μ‐Cl)}] 2 ; R = i Bu. Halogen‐bridged dimeric pincer species have been observed before 8a,8b,10. In our experiments, we propose that the bulkiness of the butyl isomers is responsible for the different coordination behaviour of the three species, with tert ‐butyl substituents generating enough steric hindrance so as to prevent association of two monomers.…”

Section: Resultssupporting

confidence: 52%

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

2014

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A family of SCS and SNS pincer compounds of the type [PdCl{C6H3‐2,6‐(CH2SR)2}] {R = tBu (3a), sBu (3b), iBu (3c)} and [NiCl2{C5H3N‐2,6‐(CH2SR)2}] {R = tBu (4a), sBu (4b)} have been prepared. Among these, complexes 3b, 3c, 4a–4c are reported for the first time. Dimeric compounds such as [NiCl{C5H3N‐2,6‐(CH2SiBu)2}μ‐Cl]2 (4c) were found in the solid state for the nickel complexes with lower steric hindrance exhibiting octahedral metal centers, whereas other nickel structures such as [NiCl2{C5H3N‐2,6‐(CH2StBu)2}(iPrOH)] (4d) could also expand their coordination number by coordinating to solvents. The single crystal X‐ray diffraction results for 4a, 4c and 4d are presented. The catalytic activity of the six compounds was studied in C–C and C–S cross‐coupling reactions under conventional heating and under microwave irradiation conditions. The palladium catalysts enabled good to excellent conversions in Suzuki–Miyaura couplings of p‐substituted halobenzenes with phenylboronic acid. Comparable yields resulted from application of the nickel complexes in the thioetherification of iodobenzene with different disulfides. The fast increase in reaction temperature associated with microwave irradiation, in combination with the robust pincer catalysts, allowed for quantitative conversions in only minutes.

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Section: Resultssupporting

confidence: 52%

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

2014

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“…Ligands 2,6-(RSCH 2 ) 2 pyridine [R = Ph ( 1 ), Cy ( 2 )] were prepared according to a modified literature method . Although 2,6-bis(phenylthiomethyl)pyridine 1 is already known in the literature for its complexes with Pd, Ni, Cu, and Ru, its chemistry with Cr remains unknown to date. The cyclohexyl derivative 2 was prepared to prevent anticipated solubility problems and would provide a system directly comparable to the previous studies on the cyclohexyl-containing SNS ligand. , …”

Section: Resultsmentioning

confidence: 99%

New Insight into the Role of the Metal Oxidation State in Controlling the Selectivity of the Cr-(SNS) Ethylene Trimerization Catalyst

et al. 2007

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The tri-and divalent complexes of the 2,6-bis(RSCH 2 )pyridine [R ) Ph, Cy] ligands have been prepared. Upon activation with MAO, both species are catalysts for ethylene oligomerization of moderate activity. However, while the trivalent catalysts produced only 1-hexene, the divalent species gave a statistical distribution of oligomers. This clear difference in catalytic behavior indicates that the two oxidation states are not interconnected during the catalytic cycle as it happens instead with other oligomerization catalytic systems. The trivalent precursor is not reduced and the divalent is not oxidized. Treatment of the trivalent catalyst precursors with either MAO or other R 3 Al species afforded intractable materials. Instead, similar reactions with the divalent complexes gave new cationic species, which have been characterized by X-ray analysis. These complexes have preserved the divalent state of chromium during the reaction and still produce, upon further activation, a statistical distribution of oligomers. This reiterates the non-interconvertibility of the di-and trivalent oxidation states and the different degree of selectivity for which they are responsible.

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“…In the present article, X-ray crystallographic and solution NMR spectroscopic characterization of the coordination chemistry of divalent group 12 metal ions with the SNS-donor ligand 2,6-bis(methylthiomethyl)pyridine ( L 1 ) is reported. As summarized in Figure , several other dithioether-derivatized lutidyl ligands have been reported. − In crystallographically characterized metal complexes, these ligands generally behave as tridentate chelating ligands, giving two five-membered rings. ,,, Bidentate binding modes have been observed in [Pd(Me)( L 1 )] 12 and [Cu( L 3 )Br(μ-Br)] 2 , where only the pyridine nitrogen and one thioether moiety bind the metal ions. The only group 12 metal ion complexes previously reported with this family of ligands are [Zn( L 2 )Br 2 ] 16 and [Cd( L 2 )Cl(μ-Cl)] 2 …”

Section: Introductionmentioning

confidence: 99%

Investigation of Group 12 Metal Complexes with a Tridentate SNS Ligand by X-ray Crystallography and ¹H NMR Spectroscopy

et al. 2005

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Two series of zinc triad complexes containing the ligand 2,6-bis(methylthiomethyl)pyridine (L1) were synthesized and characterized by X-ray crystallography and solution-state 1H NMR spectroscopy. The distorted meridional octahedral M(L1)2(ClO4)2 series includes the first structurally characterized Zn(II) and Cd(II) complexes with N2(SR2)4 coordination spheres. Coordination of HgCl2 and ZnCl2 with 1 equiv of ligand afforded mononuclear, five-coordinate species Hg(L1)Cl2 and Zn(L1)Cl2, respectively, with distorted square-pyramidal and trigonal-bipyramidal geometries. With CdCl2, the dimeric [Cd(L1)Cl(mu-Cl)]2 complex was obtained. The distorted octahedral coordination geometry of each Cd(II) center in this complex is formed by one tridentate ligand, two bridging chloride ions, and one terminal chloride ion. NMR spectra indicate that the intermolecular ligand-exchange rate of [M(L1)2](2+) decreased in the order Cd(II) > Zn(II) > Hg(II). Slow intermolecular ligand-exchange conditions on the chemical-shift time scale were found for 1:2 metal-to-ligand complexes of L(1) with Hg(II) and Zn(II) but not Cd(II). Slow intermolecular ligand-exchange conditions in acetonitrile-d(3) solutions permitting detection of (3-5)J(199Hg1H) were found for 1:1 and 1:2 Hg(ClO4)2/L1 complexes, but not for the related Cd(ClO4)2) complexes. The magnitudes of J(199Hg1H) for equivalent protons were smaller in [Hg(L1)2](2+) than in [Hg(L1)(NCCH3)x](2+). The relative intermolecular ligand-exchange rates of the zinc triad complexes investigated here suggest that the toxicity of Hg(II) is accentuated by the relative difficulty of displacing it from the coordination sites encountered.

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Complexes of late transition metals containing the mixed donor ligands 2,6-(RSCH2)2C5H3N (R = Ph, Me): Crystal structures of [{Cu(2,6-(PhSCH2)2C5H3N)(µ-X)}2] (X = Cl, Br) and [Ni(2,6-(PhSCH2)2C5H3N)Br2]

Cited by 17 publications

References 26 publications

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

New Insight into the Role of the Metal Oxidation State in Controlling the Selectivity of the Cr-(SNS) Ethylene Trimerization Catalyst

Investigation of Group 12 Metal Complexes with a Tridentate SNS Ligand by X-ray Crystallography and ¹H NMR Spectroscopy

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Complexes of late transition metals containing the mixed donor ligands 2,6-(RSCH2)2C5H3N (R = Ph, Me): Crystal structures of [{Cu(2,6-(PhSCH2)2C5H3N)(µ-X)}2] (X = Cl, Br) and [Ni(2,6-(PhSCH2)2C5H3N)Br2]

Cited by 17 publications

References 26 publications

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

Microwave‐Assisted C–C and C–S Couplings Catalysed by Organometallic Pd‐SCS or Coordination Ni‐SNS Pincer Complexes

New Insight into the Role of the Metal Oxidation State in Controlling the Selectivity of the Cr-(SNS) Ethylene Trimerization Catalyst

Investigation of Group 12 Metal Complexes with a Tridentate SNS Ligand by X-ray Crystallography and 1H NMR Spectroscopy

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Investigation of Group 12 Metal Complexes with a Tridentate SNS Ligand by X-ray Crystallography and ¹H NMR Spectroscopy