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Amidomethylation of elemental tellurium: synthesis and solid state structures of N-substituted amidomethyltellurium(IV & II) derivatives
journal contributionposted on 2010-01-01, 00:00 authored by S Misra, A K S Chauhan, P Singh, R C Srivastava, Andrew DuthieAndrew Duthie, R J Butcher
Amidomethylation of Te(0) (elemental tellurium) as well as Te(II) (aryltellurium bromide, in situ) proceeds readily under mild conditions. It involves oxidative insertion of low valent tellurium into the C-Br bond of N-substituted alpha-bromoacetamides and provides a direct synthetic route to the stable, crystalline amidomethyltellurium(IV) dibromides, (RR'NCOCH(2))(2)TeBr(2) (RR'N = Et(2)N (1b), MePhN (2b), Me(c-Hex)N (3b), O(CH(2)CH(2))(2)N (4b)) and (Et(2)NCOCH(2))ArTeBr(2) (Ar = mesityl, 5b; 1-naphthyl, 6b). Biphasic bisulfite reduction of the dialkyltellurium dibromides afforded yellow to orange coloured amido functionalized symmetrical telluroethers, (RR'NCOCH(2))(2)Te (RR'N = Et(2)N (1), MePhN (2), Me(c-Hex)N (3), O(CH(2)CH(2))(2)N (4)), of which compound 2 was isolated as a crystalline solid. Oxidation of the new dialkyltelluroethers with dihalogens (Br(2), I(2)) or SO(2)Cl(2) afforded the corresponding amidomethyltellurium(IV) dihalides, (RR'NCOCH(2))(2)TeX(2) (RR'N = Et(2)N, X = Cl (1a), Br (1b), I (1c); RR'N = MePhN, X = Cl (2a), Br (2b), I (2c); RR'N = Me(c-Hex)N, X = Cl (3a), Br (3b), I (3c); RR'N = O(CH(2)CH(2))(2)N, X = Cl (4a), Br (4b), I (4c)) that were characterized by elemental analyses and multinuclear ((1)H, (13)C, (125)Te) NMR. Single crystal X-ray data on 1b, 1c, 2, 2b, 2c, 4b, 5b and 6b suggest that the N-substituted amidomethyl group acts as a small-bite chelating ligand, via intramolecular 1,4-Te...O coordination, towards the Te(IV) centre. Steric congestion around Te(IV) due to intramolecular secondary bonding interaction(s), reduced electrophilicity of Te(II) and the partial positive charge on N due to the resonating character of the amido group presumably prevents these atoms from participating in the intermolecular associative forces in the solid state. Instead, weak C-H...O and C-H...X H-bonding interactions take centre-stage in the self assembly.