Reactions of pyridyl donors with halogens and interhalogens: an X-ray diffraction and FT-Raman investigation

Aragoni, M. Carla, Arca, Massimiliano, Devillanova, Francesco A., Hursthouse, Michael B., Huth, Susanne L., Isaia, Francesco, Lippolis, Vito, Mancini, Annalisa, Ogilvie, Helen R. and Verani, Gaetano (2005) Reactions of pyridyl donors with halogens and interhalogens: an X-ray diffraction and FT-Raman investigation. Journal of Organometallic Chemistry, 690 (8), 1923-1934. (doi:10.1016/j.jorganchem.2004.11.001).

Abstract

Three different N-donors L, namely N-ethyl-N'-3-pyridyl-imidazolidine-4,5-dione-2-thione (1), N,N'-bis(3-pyridylmethyl)-imidazolidine-4,5-dione-2-thione (2), and tetra-2-pyridyl-pyrazine (3), bearing one, two and four pyridyl substituents, respectively, have been reacted with halogens X-2 (X = Br, I) or interhalogens XY (X = I; Y = Cl, Br). CT sigma-adducts L · nXY, bearing linear N ... XY moieties (L = 3; X = I; Y = Br, I; n = 2), and salts containing the protonated cationic donors HnLn+ (L = 1 - 3; n = 1, 2, 4), counterbalanced by Cl-, Br-, I-3(-), Br-3(-), I-5(-), Br-5(-), I2Br-, I3Br4-, or ICI2- anions, have been isolated. Among the reactions products, (H1(+))Cl-, (H1(+))Br-, (H2(+))I-3(-), (H(2)3(2+))(ICl2-)(2), and 3 · 2IBr have been characterised by single-crystal X-ray diffraction. The nature of the products has been elucidated based on elemental analysis and FT-Raman spectroscopy supported by MP2 and DFT calculations.

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