Synthesis and studies on transition metal and group 15 complexes incorporating acyclic and macrocyclic chalcogenoethern ligands
Synthesis and studies on transition metal and group 15 complexes incorporating acyclic and macrocyclic chalcogenoethern ligands
A series of transition metal complexes and main group complexes incorporating thio-, seleno- and telluro-ether ligands are described.
The synthesis of the first series of Group 6 carbonyl telluroether complexes [M(CO)4(L-L)] (M = Cr, Mo or W, L-L = MeTe(CH2)3TeMe, PhTe(CH2)3TePh or o-C6H4(TeMe)2 are described along with some dithioether (L-L = MeS(CH2)2SMe, MeS(CH2)3SMe) and diselenoether (L-L = MeSe(CH2)2SeMe, MeSe(CH2)3SeMe or o-C6H4(SeMe)2) analogues. Characterisation of the complexes has been achieved using multinuclear NMR (1H 13C{1H}, 77Se{1H}, 125Te{1H} and 95Mo) and IR spectrospecies, FAB mass spectrometry and elemental analysis. The crystal structure of [Cr(CO)4{MeSe(CH2)2SeMe}] has been determined and reveals a cis disubstituted distorted octahedral geometry. Trends in the bonding in complexes of these Group 16 ligands are discussed.
The syntheses and characterisation of a series of Group 6 derivatives fac-[M(CO)3L3] (M = Mo or W, L3 = MeC(CH2SMe)3, MeC(CH2SeMe)3 or MeC(CH2TeMe)3), prepared from [M(CO)3(MeCN)3], have been investigated. IR, 1H, 13C{1H}, 77Se{1H}, 125Te{1H} and 95Mo NMR spectroscopies have been used to characterise the complexes. The complexes are prone to decomposition in solution into the tetracarbonyls, and attempts to isolate [Cr(CO)3L3] have been unsuccessful. The complexes cis-[Cr(CO)4{η2-MeC(CH2SeMe)3}] have been similarly characterised.
The complexes trans-[OsCl2(L-L)2] (L-L = o-C6H4(TeMe)2, RTe(CH2)3TeR (R = Ph or Me)) have been prepared from trans-[OsCl2(dmso)4] and the ditelluroethers in ethanol. The reaction of [OsCl2(PPh3)3 with the ditelluroethers or MeS(CH2)2SMe or MeSe(CH2)2SeMe in ethanol in the presence of NH4PF6 gave trans-[OsCl(PPh3)(L-L)2]PF6.
University of Southampton
Barton, Andrew James
9cefa49b-0891-45dd-a6a5-e4e1d31b01aa
2000
Barton, Andrew James
9cefa49b-0891-45dd-a6a5-e4e1d31b01aa
Barton, Andrew James
(2000)
Synthesis and studies on transition metal and group 15 complexes incorporating acyclic and macrocyclic chalcogenoethern ligands.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
A series of transition metal complexes and main group complexes incorporating thio-, seleno- and telluro-ether ligands are described.
The synthesis of the first series of Group 6 carbonyl telluroether complexes [M(CO)4(L-L)] (M = Cr, Mo or W, L-L = MeTe(CH2)3TeMe, PhTe(CH2)3TePh or o-C6H4(TeMe)2 are described along with some dithioether (L-L = MeS(CH2)2SMe, MeS(CH2)3SMe) and diselenoether (L-L = MeSe(CH2)2SeMe, MeSe(CH2)3SeMe or o-C6H4(SeMe)2) analogues. Characterisation of the complexes has been achieved using multinuclear NMR (1H 13C{1H}, 77Se{1H}, 125Te{1H} and 95Mo) and IR spectrospecies, FAB mass spectrometry and elemental analysis. The crystal structure of [Cr(CO)4{MeSe(CH2)2SeMe}] has been determined and reveals a cis disubstituted distorted octahedral geometry. Trends in the bonding in complexes of these Group 16 ligands are discussed.
The syntheses and characterisation of a series of Group 6 derivatives fac-[M(CO)3L3] (M = Mo or W, L3 = MeC(CH2SMe)3, MeC(CH2SeMe)3 or MeC(CH2TeMe)3), prepared from [M(CO)3(MeCN)3], have been investigated. IR, 1H, 13C{1H}, 77Se{1H}, 125Te{1H} and 95Mo NMR spectroscopies have been used to characterise the complexes. The complexes are prone to decomposition in solution into the tetracarbonyls, and attempts to isolate [Cr(CO)3L3] have been unsuccessful. The complexes cis-[Cr(CO)4{η2-MeC(CH2SeMe)3}] have been similarly characterised.
The complexes trans-[OsCl2(L-L)2] (L-L = o-C6H4(TeMe)2, RTe(CH2)3TeR (R = Ph or Me)) have been prepared from trans-[OsCl2(dmso)4] and the ditelluroethers in ethanol. The reaction of [OsCl2(PPh3)3 with the ditelluroethers or MeS(CH2)2SMe or MeSe(CH2)2SeMe in ethanol in the presence of NH4PF6 gave trans-[OsCl(PPh3)(L-L)2]PF6.
Text
757865.pdf
- Version of Record
More information
Published date: 2000
Identifiers
Local EPrints ID: 464207
URI: http://eprints.soton.ac.uk/id/eprint/464207
PURE UUID: 911de3f4-3338-4244-9975-94cfb4457796
Catalogue record
Date deposited: 04 Jul 2022 21:34
Last modified: 16 Mar 2024 19:20
Export record
Contributors
Author:
Andrew James Barton
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