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Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics

Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics
Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics
The ligands o-C6H4(CH2EMe)(2) (E = S or Se) have been prepared and characterised spectroscopically. A systematic study of the coordination chemistry of these, together with the telluroether analogue, o-C6H4(CH2TeMe)(2), with late transition metal centers has been undertaken. The planar complexes [MCl2{o-C6H4(CH2SMe)(2)}] and [M{o-C6H4(CH2EMe)(2)}(2)](PF6)(2) (M = Pd or Pt; E = S or Se), the distorted octahedral [RhCl2{o-C6H4(CH2EMe)(2)}(2)]Y (E = S or Se: Y = PF6; E = Te: Y = Cl) and [RuCl2{o-C6H4(CH2EMe)(2)}(2)] (E = S, Se or Te), the dithioether-bridged binuclear [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}] and the tetrahedral [M'{o-C6H4(CH2EMe)(2)}(2)]BF4 (M' = Cu or Ag; E = S, Se or Te) have been obtained and characterised by IR and multinuclear NMR spectroscopy (H-1, Cu-63, Se-77{H-1}, Te-125{H-1} and Pt-195), electrospray MS and microanalyses. Crystal structures of the parent o-C6H4(CH2SMe)(2) and seven complexes are described, which show three different stereoisomeric forms for the chelated ligands, as well as the first example of a bridging coordination mode in [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}]. These studies reveal the consequences of the sterically demanding o-xylyl backbone, which typically leads to unusually obtuse E-M-E chelate angles of similar to 100 degrees.
thioether macrocyclic complexes, x-ray structures, crystal-structures, coordination chemistry, homoleptic copper(i), silver (i) complexes, magnetic-resonance, ligands, selenoether, 2, 11-dithiaorthocyclophane
1477-9226
439-448
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Nirwan, Manisha
5326a14f-3c10-407b-bebe-272f53d6b9cb
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Nirwan, Manisha
5326a14f-3c10-407b-bebe-272f53d6b9cb
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Tsoureas, Nikolaos
b40771a1-8870-43bc-8989-3c6eee2f325f
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Levason, William, Nirwan, Manisha, Ratnani, Raju, Reid, Gillian, Tsoureas, Nikolaos and Webster, Michael (2007) Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics. Dalton Transactions, (4), 439-448. (doi:10.1039/b613501c).

Record type: Article

Abstract

The ligands o-C6H4(CH2EMe)(2) (E = S or Se) have been prepared and characterised spectroscopically. A systematic study of the coordination chemistry of these, together with the telluroether analogue, o-C6H4(CH2TeMe)(2), with late transition metal centers has been undertaken. The planar complexes [MCl2{o-C6H4(CH2SMe)(2)}] and [M{o-C6H4(CH2EMe)(2)}(2)](PF6)(2) (M = Pd or Pt; E = S or Se), the distorted octahedral [RhCl2{o-C6H4(CH2EMe)(2)}(2)]Y (E = S or Se: Y = PF6; E = Te: Y = Cl) and [RuCl2{o-C6H4(CH2EMe)(2)}(2)] (E = S, Se or Te), the dithioether-bridged binuclear [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}] and the tetrahedral [M'{o-C6H4(CH2EMe)(2)}(2)]BF4 (M' = Cu or Ag; E = S, Se or Te) have been obtained and characterised by IR and multinuclear NMR spectroscopy (H-1, Cu-63, Se-77{H-1}, Te-125{H-1} and Pt-195), electrospray MS and microanalyses. Crystal structures of the parent o-C6H4(CH2SMe)(2) and seven complexes are described, which show three different stereoisomeric forms for the chelated ligands, as well as the first example of a bridging coordination mode in [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}]. These studies reveal the consequences of the sterically demanding o-xylyl backbone, which typically leads to unusually obtuse E-M-E chelate angles of similar to 100 degrees.

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More information

Published date: 2007
Keywords: thioether macrocyclic complexes, x-ray structures, crystal-structures, coordination chemistry, homoleptic copper(i), silver (i) complexes, magnetic-resonance, ligands, selenoether, 2, 11-dithiaorthocyclophane

Identifiers

Local EPrints ID: 44590
URI: http://eprints.soton.ac.uk/id/eprint/44590
ISSN: 1477-9226
PURE UUID: 6037fcb0-f633-4af7-975f-bc293a691570
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 02 Mar 2007
Last modified: 16 Mar 2024 02:43

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Contributors

Author: William Levason ORCID iD
Author: Manisha Nirwan
Author: Raju Ratnani
Author: Gillian Reid ORCID iD
Author: Nikolaos Tsoureas
Author: Michael Webster

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