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Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP)

Persson, Roger LU ; Stchedroff, Marc ; Gobetto, Roberto ; Carrano, Carl J. ; Richmond, Michael G. ; Monari, Magda and Nordlander, Ebbe LU (2013) In European Journal of Inorganic Chemistry p.2447-2459
Abstract
Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by... (More)
Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N-oxide. The metastable cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable-temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid-state structures of [{Os3(CO)11}2(-PSP)] and [Os3(CO)10(-PSP)] are reported. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Tridentate ligands, Cluster compounds, Osmium, P, S ligands, Isomerization
in
European Journal of Inorganic Chemistry
issue
13
pages
2447 - 2459
publisher
John Wiley and Sons
external identifiers
  • wos:000318167500020
  • scopus:84876521287
ISSN
1099-0682
DOI
10.1002/ejic.201201403
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
id
8eb0633b-62ef-4bf0-911c-887f12d2796c (old id 3843440)
date added to LUP
2016-04-01 10:14:50
date last changed
2021-01-06 05:52:24
@article{8eb0633b-62ef-4bf0-911c-887f12d2796c,
  abstract     = {Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N-oxide. The metastable cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable-temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid-state structures of [{Os3(CO)11}2(-PSP)] and [Os3(CO)10(-PSP)] are reported.},
  author       = {Persson, Roger and Stchedroff, Marc and Gobetto, Roberto and Carrano, Carl J. and Richmond, Michael G. and Monari, Magda and Nordlander, Ebbe},
  issn         = {1099-0682},
  language     = {eng},
  number       = {13},
  pages        = {2447--2459},
  publisher    = {John Wiley and Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP)},
  url          = {http://dx.doi.org/10.1002/ejic.201201403},
  doi          = {10.1002/ejic.201201403},
  year         = {2013},
}