Organoselenium(II) and selenium(IV) compounds containing 2-(Me2NCH2)C6H4 moieties: solution behavior and solid state structure

Kulcsar, Monika, Silvestru, Anca, Silvestru, Cristian, Drake, John E., Macdonald, Charles L.B., Hursthouse, Michael B and Light, Mark E. (2005) Organoselenium(II) and selenium(IV) compounds containing 2-(Me2NCH2)C6H4 moieties: solution behavior and solid state structure. Journal of Organometallic Chemistry, 690 (13), 3217-3228. (doi:10.1016/j.jorganchem.2005.02.052).

Abstract

The cleavage of the Se-Se bond in [2-(Me₂NCH₂)C₆H₄]₂Se₂ (1) was achieved by treatment with SO₂Cl₂ (1:1 molar ratio) or elemental halogens to yield [2-(Me₂NCH-)C₆H₄]SeX [X = Cl (2), Br (3), I (4)]. Oxidation of 1 with SO₂Cl₂ (1:3 molar ratio) gave [2-(Me₂NCH₂)C₆H₄]SeCl₃ (5). [2-(Me₂NCH₂)C₆H₄]SeS(S)CNR₂ [R = Me (6), Et (7)] were prepared by reacting [2-(Me₂NCH₂)C₆H₄]SeBr with Na[S₂CNR₂] . nH₂O (R = Me, n = 2; R = Et, n = 3). The reaction of 3 with K[(SPMe₂)(SPPh₂)N] resulted in isolation of [2-(Me₂NCH₂)C₆H₄]Se-S-PMe₂=N-PPh₂=S (8). The compounds were characterized by solution NMR spectroscopy (¹H, ¹³C, ³¹P, ⁷⁷Se, 2D experiments). The solid-state molecular structures of 2, 4-8 were established by single crystal X-ray diffraction. All compounds are monomeric, with the N atom of the pendant CH₂NMe₂ arm involved in a three-center-four-electron N •••Se-X (X = halogen, S) bond. This results in a T-shaped coordination geometry for the Se(II) atom in 2, 4, 6-8. In 5, the Se(IV) atom achieves a square pyramidal coordination in the mononuclear unit. Loosely connected dimers are formed through intermolecular Se•••Cl interactions (3.40 angstrom); the overall coordination geometry being distorted octahedral. In all compounds hydrogen bonds involving halide or sulfur atoms generate supramolecular associations in crystals.

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