18794-45-1Relevant academic research and scientific papers
Copper Co-ordination to Thioether Ligands. Chemical, Spectroscopic, and Crystallographic Studies on Copper(I) Complexes of 2-(3,3-Dimethyl-2-thiabutyl)pyridine and the 2-(3,3-Dimethyl-2-thiabutyl)pyridinium Cation
Ainscough, Eric W.,Baker, Edward N.,Brodie, Andrew M.,Larsen, Nigel G.,Brown, Kevin L.
, p. 1746 - 1752 (1981)
The ligand 2-(3,3-dimethyl-2-thiabutyl)pyridine (L) and its protonated cation, 2-(3,3-dimethyl-2-thiabutyl)pyridimium ion (LH+), have been used to prepare the copper(I) complexes nBr> (n = 1 or 2) and (X = Cl or Br).Electronic and i.r. spectroscopic data for these complexes are presented, and the chemical relationships between them discussed.The crystal and molecular structures of and have been determined by single crystal X-ray diffraction techniques, from diffractometer data.Crystals of are monoclinic, space group P21/n, with a = 16.927(3), b = 8.867(1), c = 15.371(2) Angstroem, β = 100.61(1) deg, and Z = 4.Crystals of are also monoclinic, space group P21/n, with a = 15.700(3), b = 9.038(3), c = 9.926(2) Angstroem, β = 98.66(1) deg, and Z = 2.After full-matrix least-squares refinement final R values are 0.066 (for 2 032 observed reflections) and 0.047 (for 1 538 observed reflections) respectively.The complex is monomeric, the distorted tetrahedral geometry round the copper atom being completed by a bromide ion , the pyridyl nitrogen and thioether sulphur of a bidentate ligand L , and the thioether sulphur of a unidentate ligand L .The complex exists as a centrosymmetric dimer with the distorted tetrahedral copper(I) centres dibromo bridged .The two remaining co-ordination positions round each copper are occupied by a terminal romide ion and the thioether sulphur of an LH+ cation.
The methyl group as a source of structural diversity in heterocyclic chemistry: Side chain functionalization of picolines and related heterocycles
Mamane, Victor,Aubert, Emmanuel,Fort, Yves
, p. 7294 - 7300 (2008/02/11)
(Chemical Equation Presented) The reaction of 2-picoline at the methyl group with NDA and KDA followed by dimethyldisulfide trapping furnished, respectively, dithioacetals and trithioortho esters with high selectivity. The method was successfully applied to other methyl-substituted pyridines, quinolines, and pyrazines. Dithioketals were prepared by a one-pot procedure involving the reaction of metalated 2-picoline with 2 equiv of dimethyldisulfide followed by in situ trapping with a second electrophile. All of the generated thio-substituted compounds were efficiently transformed in presence of mercury salts or under oxidizing conditions to other functional groups comprising aldehydes, ketones, ketals, thiol esters, orthoesters, and esters.
Palladium(II) allyl complexes with nitrogen-sulfur bidentate ligands. Substituent effects in the mechanism of allyl amination
Canovese, Luciano,Visentin, Fabiano,Uguagliati, Paolo,Chessa, Gavino,Pesce, Andrea
, p. 61 - 71 (2007/10/03)
The reactivity of palladium(II) allyl complexes containing the nitrogen-sulfur bidentate ligand N-SR (N-SR=2-(phenylthiomethyl)pyridine, 2-(phenylthiomethyl)-6-methylpyridine, 2-(tert-butylthiomethyl)pyridine) was studied in CHCl3 in the presence of the activated olefin fumaronitrile (fn). The stepwise mechanism involves a fast pre-equilibrium in which the N-SR ligand is displaced by the amine with formation of an inert bis-amino allyl species and concomitant rate-determining bimolecular attack of the amine on the coordinated allyl moiety to give the allylamine and the olefin-stabilized Pd(0) complexes [Pd(η2-fn)(N-SR)]. The influence of the substituents at the allyl fragment and at the nitrogen-sulfur ligand is rationalized together with the fluxional behavior in solution.
