Synthesis and coordination chemistry of telluroether ligands
Synthesis and coordination chemistry of telluroether ligands
The syntheses of the ditelluroether complexes [Mn(CO)3(L-L)X] {X = Cl, Br or I; L-L = MeTe(CH2)3TeMe, PhTe(CH2)3TePh and o-C6H4(TeMe)2} and [Re(CO)3(L-L)X] (X = Cl or Br) are described, along with the crystal structures of [M(CO)3{o-C6H4(TeMe)2}Cl] (M = Mn or Re). Detailed comparisons of the spectroscopic data for these and analogous thio- and selenoether species have revealed that the telluroether compounds show significantly enhanced σ-donation compared to the lighter chalcogens. The analogous tripodal complexes [Mn(CO)3(L3)][CF3SO3] {L3 = MeC(CH2EMe)3 (E = S, Se or Te) and MeC(CH2TePh)3}, have been prepared and structurally characterised. Increased σ-donation is again observed down group 16, with significantly enhanced donation by the MeC(CH2TeMe)3 ligand.
A range of homoleptic platinum group metal and group 11 metal complexes has been prepared with the group 16 tripodal ligands and a range of coordination modes observed. The species [M(L3)2][PF6]2 {M = Pd or Pt; L3 = MeC(CH2EMe)3 (E = Se or Te) and MeC(CH2TePh)3} have been synthesised, with the crystal structure of [Pt{MeC(CH2SeMe)3}2][PF6]2 revealing distorted square planar Se4 coordination at Pt(II) with the remaining arm of each tripod uncoordinated. For the hexaseleno- and hexatelluroether complexes, [Ru(L3)2][CF3SO3]2, both ligands adopt a facial arrangement, confirmed by the X-ray crystal structures of thio- and selenoether analogues. The group 11 metal complexes [Cu(L3)2][PF6], [Ag{MeC(CH2TeR)3}2][CF3SO3] (R = Me or Ph) and [Ag{MeC(CH2SeMe)3}][CF3SO3] have also been synthesised. The structure of the Ag(I) seleoether species reveals a distorted trigonal planar geometry at the metal centre derived from one bidentate selenoether and one monodentate selenoether ligand. These units are then linked to adjacent Ag(I) ions to give a one dimensional linear chain cation.
University of Southampton
Orchard, Simon David
514a4c34-c224-4b0b-b4e3-da4ec7e7521b
2000
Orchard, Simon David
514a4c34-c224-4b0b-b4e3-da4ec7e7521b
Orchard, Simon David
(2000)
Synthesis and coordination chemistry of telluroether ligands.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The syntheses of the ditelluroether complexes [Mn(CO)3(L-L)X] {X = Cl, Br or I; L-L = MeTe(CH2)3TeMe, PhTe(CH2)3TePh and o-C6H4(TeMe)2} and [Re(CO)3(L-L)X] (X = Cl or Br) are described, along with the crystal structures of [M(CO)3{o-C6H4(TeMe)2}Cl] (M = Mn or Re). Detailed comparisons of the spectroscopic data for these and analogous thio- and selenoether species have revealed that the telluroether compounds show significantly enhanced σ-donation compared to the lighter chalcogens. The analogous tripodal complexes [Mn(CO)3(L3)][CF3SO3] {L3 = MeC(CH2EMe)3 (E = S, Se or Te) and MeC(CH2TePh)3}, have been prepared and structurally characterised. Increased σ-donation is again observed down group 16, with significantly enhanced donation by the MeC(CH2TeMe)3 ligand.
A range of homoleptic platinum group metal and group 11 metal complexes has been prepared with the group 16 tripodal ligands and a range of coordination modes observed. The species [M(L3)2][PF6]2 {M = Pd or Pt; L3 = MeC(CH2EMe)3 (E = Se or Te) and MeC(CH2TePh)3} have been synthesised, with the crystal structure of [Pt{MeC(CH2SeMe)3}2][PF6]2 revealing distorted square planar Se4 coordination at Pt(II) with the remaining arm of each tripod uncoordinated. For the hexaseleno- and hexatelluroether complexes, [Ru(L3)2][CF3SO3]2, both ligands adopt a facial arrangement, confirmed by the X-ray crystal structures of thio- and selenoether analogues. The group 11 metal complexes [Cu(L3)2][PF6], [Ag{MeC(CH2TeR)3}2][CF3SO3] (R = Me or Ph) and [Ag{MeC(CH2SeMe)3}][CF3SO3] have also been synthesised. The structure of the Ag(I) seleoether species reveals a distorted trigonal planar geometry at the metal centre derived from one bidentate selenoether and one monodentate selenoether ligand. These units are then linked to adjacent Ag(I) ions to give a one dimensional linear chain cation.
Text
757847.pdf
- Version of Record
More information
Published date: 2000
Identifiers
Local EPrints ID: 464201
URI: http://eprints.soton.ac.uk/id/eprint/464201
PURE UUID: d5cbc985-0feb-409a-9947-1737ba1affe8
Catalogue record
Date deposited: 04 Jul 2022 21:32
Last modified: 16 Mar 2024 19:20
Export record
Contributors
Author:
Simon David Orchard
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