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).
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The cleavage of the Se-Se bond in [2-(Me2NCH2)C6H4](2)Se-2 (1) was achieved by treatment with SO2Cl2 (1:1 molar ratio) or elemental halogens to yield [2-(Me NCH-)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] . nH(2)O (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 (H-1, C-13, P-31, Se-77, 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 center dot center dot center dot 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.
|Keywords:||hypervalent organoselenium compounds, nmr studies, crystal structures asymmetric addition-reactions, x-ray structures, glutathione-peroxidase, intramolecular interactions, diethylzincaddition, molecular-structures, organochalcogen se, chiral diselenides, nmr-spectroscopy, te compounds|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||University Structure - Pre August 2011 > School of Chemistry
|Date Deposited:||03 Mar 2006|
|Last Modified:||01 Jun 2011 11:05|
|Contributors:||Kulcsar, Monika (Author)
Silvestru, Anca (Author)
Silvestru, Cristian (Author)
Drake, John E. (Author)
Macdonald, Charles L.B. (Author)
Hursthouse, Michael B (Author)
Light, Mark E. (Author)
|Date:||1 July 2005|
|Contact Email Address:||firstname.lastname@example.org|
|RDF:||RDF+N-Triples, RDF+N3, RDF+XML, Browse.|
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