RESUMO
Four cationic C,C-(NHC-cyanoalkyl)-nickel(ii) metallacyclic complexes, [Ni{Me-NHC-CH2CH(CN)}(NCMe)](PF6) (2a), [Ni{Mes-NHC-CH2CH(CN)}(NCMe)](PF6) (2b), [Ni{Mes-NHC-(CH2)2CH(CN)}(NCMe)](PF6) (2c) and [Ni{DiPP-NHC-(CH2)2CH(CN)}(NCMe)](PF6) (2d), were prepared by the removal of the Cp ligand under acidic conditions at 0 °C from the corresponding half-sandwich nickelacycles [NiCp{R-NHC-(CH2)nCH(CN)}] (1a-1d; Cp = η5-C5H5; n = 1 or 2; R-NHC-(CH2)nCH(CN) = 1-R-3-[(CH2)nCH(CN)]-imidazol-2-ylidene). Full characterization of 2a-d by 1H and 13C{1H} NMR spectroscopy in CD3CN and pyridine-d5, ATR-FTIR spectroscopy, mass spectrometry, and CHN microanalyses established the presence of only one acetonitrile ligand per nickel atom in the solid state. A DFT structural study conducted on the cations of the methyl-substituted 5-membered nickelacycle 2a and the mesityl-substituted 6-membered cycle 2c found a small energetic cost (ΔG = 7-12 kcal mol-1) for the loss of one acetonitrile ligand from the square-planar structures existing in solution, that should be easily amenable upon solvent evaporation (ΔG = 14 kcal mol-1 in the case of 2c). Two structures with one acetonitrile ligand could be optimized in both cases: (i) a truly T-shaped 14-electron structure with an end-on acetonitrile ligand, and (ii) a masked T-shaped structure stabilized by the π-coordination of the dangling CN group of the metallated alkyl chain, the latter being favoured by 2.4 kcal mol-1 in the case of the flexible 6-membered ring 2c. A comparison of calculated vibrational frequencies with experimental FTIR spectra ruled out π-coordination of the dangling CN group as a ν(C[triple bond, length as m-dash]N) band at low frequency was absent. Complexes 2a-d thus probably exist as rare three-coordinate T-shaped 14-electron species in the solid state. Their catalytic activity was studied for the direct arylation of azoles, and 2c proved to be moderately active for the coupling of benzothiazole with aryl iodides. Mechanistic insights suggest that competing processes or a radical process catalysed by nickel particles could follow an initial reduction of 2c by the dimerization of a sacrificial amount of benzothiazole.
RESUMO
Chelating bis-N-heterocyclic carbene (bis-NHC) complexes of iron(ii) containing pyridyl ligands have been prepared by the reaction of [FeCl2L] [L = bipy (1), phen (2)] with [LiN(SiMe3)2] and a bis(imidazolium) salt. The [Fe(bis-NHC)L(I)2] complexes were active pre-catalysts in the oxidation of 1-phenylethanol with tert-butyl hydroperoxide in neat conditions, affording a quantitative yield of acetophenone in 4.5 h. The catalyst could be reused up to six cycles giving a turnover number (TON) of 1500. Various secondary alcohols, both aromatic and aliphatic were selectivity oxidised to the corresponding ketones in excellent yields. Compound 1 is stable in acetonitrile solution for ca. 4 h, although after 16 h, it evolves to a mixture of [Fe(bis-NHC)(bipy)2]I2 (3), [Fe(bipy)3](2+) and bis-imidazolium salt. The molecular structure of 3 has been determined by X-ray diffraction studies.
RESUMO
New Cu(ii)/Ni(ii) heterodinuclear complexes with salphen-type ligands were synthesised via a stepwise template method. DFT studies were performed to understand their electronic properties, showing localisation of the HOMO on the Ni(ii) fragment, while in the oxidised species the spin density was high at some carbon phenolate atoms. These new complexes were potentiodynamically electropolymerised on glassy carbon and platinum. Atomic force microscopy was used to evaluate the influence of the metal centres on the morphology of the polymers, revealing how the presence of Cu(ii) increased the surface roughness. The oxygen reduction reaction was observed on both glassy carbon and platinum modified electrodes in neutral medium.
