The University of Southampton
University of Southampton Institutional Repository

Reactions of hybrid organotellurium ligands 1-(4-methoxyphenyltelluro)-2- 3-(6-methyl-2-pyridyl) propoxy ethane (L-1) and 1-ethylthio-2- 2-thienyltelluro ethane (L-2) with mercury(II) bromide: formation of complexes and their decomposition

Reactions of hybrid organotellurium ligands 1-(4-methoxyphenyltelluro)-2- 3-(6-methyl-2-pyridyl) propoxy ethane (L-1) and 1-ethylthio-2- 2-thienyltelluro ethane (L-2) with mercury(II) bromide: formation of complexes and their decomposition
Reactions of hybrid organotellurium ligands 1-(4-methoxyphenyltelluro)-2- 3-(6-methyl-2-pyridyl) propoxy ethane (L-1) and 1-ethylthio-2- 2-thienyltelluro ethane (L-2) with mercury(II) bromide: formation of complexes and their decomposition
Two tellurium ligands 1-(4-methoxyphenyltelluro)-2-[3 -(6-methyl-2-pyridyl)propoxy]ethane (L-1) and 1-ethylthio-2-[2-thienyltelluro]ethane (L-2) have been synthesized by reacting nucleophiles [4-MeO-C6H4Te-] and [C4H3S-2-Te-] with 2-[3-(6-methyl-2-pyridyl)propoxy]ethylchlo ride and chloroethyl ethyl sulfide, respectively. Both the ligands react with HgBr2 resulting in complexes of stoichiometry [HgBr2 (.) L-1/L-2] (1/4), which show characteristic NMR (H-1 and C-13{H-1}). On crystallization of I from acetone-hexane (2:1) mixture, the cleavage of L-1 occurs resulting in 4-MeOC6H4HgBr (2) and [RTe+ -> HgBr2]Br- (3) (where R = -CH2CH2OCH2CH2CH2-(2-(6-CH3-C5H3N))). The 2 is characterized by X-ray diffraction on its single crystal. It is a linear molecule and is the first such system which is fully characterized structurally. The Hg-C and Hg-Br bond lengths are 2.085(6) and 2.4700(7) angstrom. The distance of four bromine atoms (3.4041(7)-3.546(7) angstrom) around Hg (cis to C) is greater than the sum of van der Waal's radii 3.30 angstrom. This mercury promoted cleavage is observed for an acyclic ligand of RArTe type for the first time and is unique, as there appears to be no strong intramolecular interaction to stabilize the cleavage products. The 4 on crystallization shows the cleavage of organotellurium ligand L-2 and formation of a unique complex [(EtS(CH2)(2)SEt)HgBr(mu-Br)Hg(Br)(mu-Br)(2)Hg(Br)(mu-Br)BrHg(EtS(CH2)(2 )SEt)] (.) 2HgBr(2) (5), which has been characterized by single crystal structure determination and H-1 and C-13 {H-1} NMR spectra. The elemental tellurium and [C4H3SCH2](2) are the other products of dissociation as identified by NMR (proton and carbon-13). The cleavage appears to be without any transmetalation and probably first of its kind. The centrosymmetric structure of 5 is unique as it has [HgBr3](-) unit, one Hg in distorted tetrahedral geometry and one in pseudo-trigonal bipyramidal one. The molecule of 5 may also be described as having [(EtSCH2CH2SEt)HgBr](+) [HgBr3](-) units, which dimerize and co-crystallize with two HgBr, moieties. There are very weak Hg (...) Br interactions between co-crystallized HgBr, units and rest of the molecule. [Hg(3)-Br(1)/Hg(3)-Br(4) = 3.148(1)/3.216(1) angstrom]. The bridging Hg (...) Br distances, Hg(2)-Br(4)', Hg(2)'-Br(4) and Hg(1)-Br(2), are from 2.914(1) to 3.008(1) angstrom.
tellurium ligands, 1-(4-methoxyphenyltelluro)-2-[3-(6-methyl-2-pyridyl)propoxylethane, 1-ethylthio-2-[2-thienyltelluro]ethane, mercury complexes, decomposition, crystal structuresx-ray-diffraction, organic tellurides, chemistry, chloride, crystal
0020-1693
912-918
Singh, Garima
968f9825-9305-4532-8f2c-98118db57dc4
Bali, Sumit
f8c555fb-0ff1-4986-bbff-8d86ee3fd984
Singh, Ajai K.
28b56ec1-f3bf-4860-ab62-d6aa1eb96f6c
Drake, John E.
6de1350f-4eb6-4ca7-b796-947f4fec467d
Macdonald, Charles L.B.
00b29e53-a2f5-4bbe-8e56-24528eeb7e6f
Hursthouse, M.B.
427032bc-428c-4396-adb0-b38e87e908e7
Little, M E.
9d97463d-1f1b-4f52-8666-b239718c75f4
Singh, Garima
968f9825-9305-4532-8f2c-98118db57dc4
Bali, Sumit
f8c555fb-0ff1-4986-bbff-8d86ee3fd984
Singh, Ajai K.
28b56ec1-f3bf-4860-ab62-d6aa1eb96f6c
Drake, John E.
6de1350f-4eb6-4ca7-b796-947f4fec467d
Macdonald, Charles L.B.
00b29e53-a2f5-4bbe-8e56-24528eeb7e6f
Hursthouse, M.B.
427032bc-428c-4396-adb0-b38e87e908e7
Little, M E.
9d97463d-1f1b-4f52-8666-b239718c75f4

Singh, Garima, Bali, Sumit, Singh, Ajai K., Drake, John E., Macdonald, Charles L.B., Hursthouse, M.B. and Little, M E. (2005) Reactions of hybrid organotellurium ligands 1-(4-methoxyphenyltelluro)-2- 3-(6-methyl-2-pyridyl) propoxy ethane (L-1) and 1-ethylthio-2- 2-thienyltelluro ethane (L-2) with mercury(II) bromide: formation of complexes and their decomposition. Inorganica Chimica Acta, 358 (4), 912-918. (doi:10.1016/j.ica.2004.10.021).

Record type: Article

Abstract

Two tellurium ligands 1-(4-methoxyphenyltelluro)-2-[3 -(6-methyl-2-pyridyl)propoxy]ethane (L-1) and 1-ethylthio-2-[2-thienyltelluro]ethane (L-2) have been synthesized by reacting nucleophiles [4-MeO-C6H4Te-] and [C4H3S-2-Te-] with 2-[3-(6-methyl-2-pyridyl)propoxy]ethylchlo ride and chloroethyl ethyl sulfide, respectively. Both the ligands react with HgBr2 resulting in complexes of stoichiometry [HgBr2 (.) L-1/L-2] (1/4), which show characteristic NMR (H-1 and C-13{H-1}). On crystallization of I from acetone-hexane (2:1) mixture, the cleavage of L-1 occurs resulting in 4-MeOC6H4HgBr (2) and [RTe+ -> HgBr2]Br- (3) (where R = -CH2CH2OCH2CH2CH2-(2-(6-CH3-C5H3N))). The 2 is characterized by X-ray diffraction on its single crystal. It is a linear molecule and is the first such system which is fully characterized structurally. The Hg-C and Hg-Br bond lengths are 2.085(6) and 2.4700(7) angstrom. The distance of four bromine atoms (3.4041(7)-3.546(7) angstrom) around Hg (cis to C) is greater than the sum of van der Waal's radii 3.30 angstrom. This mercury promoted cleavage is observed for an acyclic ligand of RArTe type for the first time and is unique, as there appears to be no strong intramolecular interaction to stabilize the cleavage products. The 4 on crystallization shows the cleavage of organotellurium ligand L-2 and formation of a unique complex [(EtS(CH2)(2)SEt)HgBr(mu-Br)Hg(Br)(mu-Br)(2)Hg(Br)(mu-Br)BrHg(EtS(CH2)(2 )SEt)] (.) 2HgBr(2) (5), which has been characterized by single crystal structure determination and H-1 and C-13 {H-1} NMR spectra. The elemental tellurium and [C4H3SCH2](2) are the other products of dissociation as identified by NMR (proton and carbon-13). The cleavage appears to be without any transmetalation and probably first of its kind. The centrosymmetric structure of 5 is unique as it has [HgBr3](-) unit, one Hg in distorted tetrahedral geometry and one in pseudo-trigonal bipyramidal one. The molecule of 5 may also be described as having [(EtSCH2CH2SEt)HgBr](+) [HgBr3](-) units, which dimerize and co-crystallize with two HgBr, moieties. There are very weak Hg (...) Br interactions between co-crystallized HgBr, units and rest of the molecule. [Hg(3)-Br(1)/Hg(3)-Br(4) = 3.148(1)/3.216(1) angstrom]. The bridging Hg (...) Br distances, Hg(2)-Br(4)', Hg(2)'-Br(4) and Hg(1)-Br(2), are from 2.914(1) to 3.008(1) angstrom.

Full text not available from this repository.

More information

Published date: 1 March 2005
Keywords: tellurium ligands, 1-(4-methoxyphenyltelluro)-2-[3-(6-methyl-2-pyridyl)propoxylethane, 1-ethylthio-2-[2-thienyltelluro]ethane, mercury complexes, decomposition, crystal structuresx-ray-diffraction, organic tellurides, chemistry, chloride, crystal

Identifiers

Local EPrints ID: 20910
URI: http://eprints.soton.ac.uk/id/eprint/20910
ISSN: 0020-1693
PURE UUID: 668106ef-c23c-4b23-ad5c-9650c0c7fd55

Catalogue record

Date deposited: 01 Mar 2006
Last modified: 15 Jul 2019 19:25

Export record

Altmetrics

Contributors

Author: Garima Singh
Author: Sumit Bali
Author: Ajai K. Singh
Author: John E. Drake
Author: Charles L.B. Macdonald
Author: M.B. Hursthouse
Author: M E. Little

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×