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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Description/Abstract
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.
| Item Type: | Article |
|---|---|
| ISSNs: | 0022-328X (print) |
| Related URLs: | |
| 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 |
| Item ID: | 20841 |
| 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 |
| Status: | Published |
| Contact Email Address: | cristi@chem.ubbcluj.ro |
| URI: | http://eprints.soton.ac.uk/id/eprint/20841 |
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