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Volumn 48, Issue 3, 2009, Pages 555-558

A simple preparation of pyridine-derived N-heterocyclic carbenes and their transformation into bridging ligands by orthometalation

Author keywords

C H activation; Carbenes; Cluster compounds; Nitrogen heterocycles; Ruthenium

Indexed keywords

ACTIVATION ANALYSIS; ALKALINITY; CARBON MONOXIDE; CHEMICAL REACTIONS; RUTHENIUM;

EID: 58249115085     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200804945     Document Type: Article
Times cited : (48)

References (46)
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    • A toluene solution of K[(Me3Si)2N, 315 μL, 0.5 M, 0.156 mmol) was added to a mixture of [Ru3(CO) 12, 100 mg, 0.156 mmol) and N-methylpyridinium triflate (38 mg, 0.156 mmol) in THF (20 mL, The mixture was stirred at room temperature until the consumption of the starting ruthenium complex was confirmed by IR spectroscopy (10 h, The solvent was removed under reduced pressure and the residue was extracted into toluene (20 mL) to give a red solution and a brown solid. The solution was concentrated and purified by preparative thin-layer chromatography (silica gel, Elution with dichloromethane/hexane (1:4) afforded compound 1 10 mg, 10, as a red-orange band. A dark brown residue remained uneluted on the plate baseline. Compounds 2 and 3 were prepared in similar yields from the respective appropriate N-methylpicolinium triflate
    • 12] (100 mg, 0.156 mmol) and N-methylpyridinium triflate (38 mg, 0.156 mmol) in THF (20 mL). The mixture was stirred at room temperature until the consumption of the starting ruthenium complex was confirmed by IR spectroscopy (10 h). The solvent was removed under reduced pressure and the residue was extracted into toluene (20 mL) to give a red solution and a brown solid. The solution was concentrated and purified by preparative thin-layer chromatography (silica gel). Elution with dichloromethane/hexane (1:4) afforded compound 1 (10 mg, 10%) as a red-orange band. A dark brown residue remained uneluted on the plate baseline. Compounds 2 and 3 were prepared in similar yields from the respective appropriate N-methylpicolinium triflate.
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    • Spectroscopic data: a) 1: 1H NMR (CDCl3, δ, 8.28 (d, J, 6.5 Hz, 1H, 7.99 (d, J, 6.5 Hz, 1H, 6.82 (t, J, 6.5 Hz, 1H, 4.09 (s, 3H, 18.08 ppm (s, 1H, IR (CH 2Cl2, ṽ(CO, 2079 (m, 2052 (s, 2013 (vs, 1981 (m, sh, 1950 cm-1 (w, sh, b) 2: 1H NMR (CDCl3, δ, 8.18 (d, J, 7.5 Hz, 1H, 6.69 (d, J, 7.5 Hz, 1H, 4.07 (s, 3H, 3.68 (s, 3H, 17.95 ppm (s, 1H, IR (CH 2Cl2, ṽ(CO, 2078 (m, 2049 (s, 2013 (vs, 1981 (m, sh, 1949 cm-1 (w, sh, c) 3: 1H NMR (CDCl3, δ, 7.95 (d, J, 6.0 Hz, 1H, 6.84 (d, J, 6.0 Hz, 1H, 4.05 (s, 3H, 2.54 (s, 3H, 17.76 ppm (s, 1H, 13C NMR (DEPT, CDCl3, δ, 177.7 (C, 174.5 (C, 146.5 (C, 143.1 (CH, 115.8 (CH, 50.7 (CH3, 26.8 ppm (CH3, IR CH
    • -1 (w, sh).
  • 34
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    • Crystal data for 3·(hexane)0.25: C 16H9NO9Ru3·0.25(C 6H14, Mr, 680.46; crystal size 0.12 x 0.07 x 0.02 mm; triclinic; space group P1; a, 9.630(2, b, 9.910(2, c, 12.358(3) Å; α, 80.472(1, β, 71.785(1, γ, 79.735(1)°; V, 1094.7(4) Å3; Z, 2; ρcalcd, 2.064 g cm-3; F(000, 650; μ, 2.090 mm-1; 10691 reflections measured, 3640 independent reflections; R1, 0.0609 and wR2, 0.1996 all data, CCDC 703646 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • 2 = 0.1996 (all data). CCDC 703646 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
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    • The experimental details of the DFT calculations, as well as tables containing computed interatomic distances, NPA atomic charges, and Cartesian atomic coordinates for all optimized stationary points are contained in the Supporting Information
    • The experimental details of the DFT calculations, as well as tables containing computed interatomic distances, NPA atomic charges, and Cartesian atomic coordinates for all optimized stationary points are contained in the Supporting Information.


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