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

Organoselenium(II) and selenium(IV) compounds containing 2-(Me2NCH2)C6H4 moieties: solution behavior and solid state structure
Organoselenium(II) and selenium(IV) compounds containing 2-(Me2NCH2)C6H4 moieties: solution behavior and solid state structure
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.
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
0022-328X
3217-3228
Kulcsar, Monika
e6d5b744-d5f1-4f57-ae1e-2c7fd134bb7c
Silvestru, Anca
7a22b88c-0f7a-4648-9921-6c0bfe060f00
Silvestru, Cristian
3c746450-778d-4eab-a0db-cc9967b0b890
Drake, John E.
6de1350f-4eb6-4ca7-b796-947f4fec467d
Macdonald, Charles L.B.
00b29e53-a2f5-4bbe-8e56-24528eeb7e6f
Hursthouse, Michael B
49957cda-627e-45ca-a3b8-0d604489bab6
Light, Mark E.
13b5eb33-3114-4fb7-8500-90ce69e9933c
Kulcsar, Monika
e6d5b744-d5f1-4f57-ae1e-2c7fd134bb7c
Silvestru, Anca
7a22b88c-0f7a-4648-9921-6c0bfe060f00
Silvestru, Cristian
3c746450-778d-4eab-a0db-cc9967b0b890
Drake, John E.
6de1350f-4eb6-4ca7-b796-947f4fec467d
Macdonald, Charles L.B.
00b29e53-a2f5-4bbe-8e56-24528eeb7e6f
Hursthouse, Michael B
49957cda-627e-45ca-a3b8-0d604489bab6
Light, Mark E.
13b5eb33-3114-4fb7-8500-90ce69e9933c

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).

Record type: Article

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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More information

Published date: 1 July 2005
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

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Local EPrints ID: 20841
URI: http://eprints.soton.ac.uk/id/eprint/20841
ISSN: 0022-328X
PURE UUID: 3b37c731-ba6a-4c72-87d1-26fc0ea028d2

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Date deposited: 03 Mar 2006
Last modified: 15 Jul 2019 19:25

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Contributors

Author: Monika Kulcsar
Author: Anca Silvestru
Author: Cristian Silvestru
Author: John E. Drake
Author: Charles L.B. Macdonald
Author: Michael B Hursthouse
Author: Mark E. Light

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